CN1812878A - Thermoplastic powder material system for appearance models from 3d prinitng systems - Google Patents
Thermoplastic powder material system for appearance models from 3d prinitng systems Download PDFInfo
- Publication number
- CN1812878A CN1812878A CNA2004800183609A CN200480018360A CN1812878A CN 1812878 A CN1812878 A CN 1812878A CN A2004800183609 A CNA2004800183609 A CN A2004800183609A CN 200480018360 A CN200480018360 A CN 200480018360A CN 1812878 A CN1812878 A CN 1812878A
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- China
- Prior art keywords
- fluid
- ester
- glycol
- particle
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000463 material Substances 0.000 title claims abstract description 99
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 94
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 94
- 239000000843 powder Substances 0.000 title claims abstract description 78
- 239000012530 fluid Substances 0.000 claims abstract description 237
- 239000000853 adhesive Substances 0.000 claims abstract description 118
- 230000001070 adhesive effect Effects 0.000 claims abstract description 117
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 238000010146 3D printing Methods 0.000 claims abstract description 32
- -1 polyactide Polymers 0.000 claims description 164
- 239000002245 particle Substances 0.000 claims description 144
- 239000008187 granular material Substances 0.000 claims description 92
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 91
- 239000002904 solvent Substances 0.000 claims description 64
- 150000005690 diesters Chemical class 0.000 claims description 54
- 239000000835 fiber Substances 0.000 claims description 52
- 239000000945 filler Substances 0.000 claims description 50
- 238000007046 ethoxylation reaction Methods 0.000 claims description 47
- 229920001577 copolymer Polymers 0.000 claims description 41
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 40
- 150000002148 esters Chemical class 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000009835 boiling Methods 0.000 claims description 34
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 30
- 125000004386 diacrylate group Chemical group 0.000 claims description 30
- 239000002202 Polyethylene glycol Substances 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 23
- 229920002472 Starch Polymers 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- 239000008107 starch Substances 0.000 claims description 22
- 235000019698 starch Nutrition 0.000 claims description 22
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 21
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 20
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 229920001451 polypropylene glycol Polymers 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 18
- 229920002678 cellulose Polymers 0.000 claims description 18
- 235000010980 cellulose Nutrition 0.000 claims description 18
- 239000004568 cement Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 239000001913 cellulose Substances 0.000 claims description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- 229920002125 Sokalan® Polymers 0.000 claims description 16
- 230000003213 activating effect Effects 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 16
- 239000004584 polyacrylic acid Substances 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 15
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 15
- 150000002921 oxetanes Chemical class 0.000 claims description 15
- 150000003505 terpenes Chemical class 0.000 claims description 15
- 235000007586 terpenes Nutrition 0.000 claims description 15
- 229940117958 vinyl acetate Drugs 0.000 claims description 15
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 14
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 14
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 14
- 229920003023 plastic Polymers 0.000 claims description 14
- 239000004033 plastic Substances 0.000 claims description 14
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 13
- 150000001491 aromatic compounds Chemical class 0.000 claims description 13
- 229940052303 ethers for general anesthesia Drugs 0.000 claims description 13
- 150000002576 ketones Chemical class 0.000 claims description 13
- 239000002798 polar solvent Substances 0.000 claims description 13
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 13
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 229920000881 Modified starch Polymers 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 235000019426 modified starch Nutrition 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 12
- 239000004368 Modified starch Substances 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229940051250 hexylene glycol Drugs 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 10
- 229930188620 butyrolactone Natural products 0.000 claims description 10
- 235000011187 glycerol Nutrition 0.000 claims description 10
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000006254 rheological additive Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 9
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 9
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 9
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical group CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 229920000609 methyl cellulose Polymers 0.000 claims description 8
- 235000010981 methylcellulose Nutrition 0.000 claims description 8
- 239000001923 methylcellulose Substances 0.000 claims description 8
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 8
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 7
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 7
- ZKYCLDTVJCJYIB-UHFFFAOYSA-N 2-methylidenedecanamide Chemical compound CCCCCCCCC(=C)C(N)=O ZKYCLDTVJCJYIB-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 7
- 101000598921 Homo sapiens Orexin Proteins 0.000 claims description 7
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 claims description 7
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 7
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 150000001720 carbohydrates Chemical class 0.000 claims description 7
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
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- 239000010440 gypsum Substances 0.000 claims description 7
- 229910052602 gypsum Inorganic materials 0.000 claims description 7
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 7
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 7
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- 239000010695 polyglycol Substances 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
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- RPZANUYHRMRTTE-UHFFFAOYSA-N 2,3,4-trimethoxy-6-(methoxymethyl)-5-[3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxyoxane;1-[[3,4,5-tris(2-hydroxybutoxy)-6-[4,5,6-tris(2-hydroxybutoxy)-2-(2-hydroxybutoxymethyl)oxan-3-yl]oxyoxan-2-yl]methoxy]butan-2-ol Chemical compound COC1C(OC)C(OC)C(COC)OC1OC1C(OC)C(OC)C(OC)OC1COC.CCC(O)COC1C(OCC(O)CC)C(OCC(O)CC)C(COCC(O)CC)OC1OC1C(OCC(O)CC)C(OCC(O)CC)C(OCC(O)CC)OC1COCC(O)CC RPZANUYHRMRTTE-UHFFFAOYSA-N 0.000 claims description 6
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 6
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- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 6
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/251—Mica
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/253—Cellulosic [e.g., wood, paper, cork, rayon, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
- Y10T428/257—Iron oxide or aluminum oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/259—Silicic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Civil Engineering (AREA)
- Mechanical Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
Abstract
The present invention is directed to a materials system and method that satisfies the need for a quick, reliable, safe, and inexpensive method for producing both appearance models and small numbers of functional parts in an office environment. The materials system includes thermoplastic particulate material, allowing the fabrication of appearance models and fonctional parts that are accurately defined, are strong and tough without being brittle, and have smooth surface finishes with, optionally, thin walls. Thermoplastic materials are used very widely for engineering and consumer products. These materials, therefore, are particularly attractive for prototyping, because they are typically also used in the final manufacturing method. In an aspect, the invention features a powder adapted for three-dimensional printing. The powder includes a blend of a thermoplastic particulate material, and an adhesive particulate material, with the adhesive particulate material being adapted to bond the thermoplastic particulate material when a fluid activates the adhesive particulate material.
Description
Related application
The application requires the rights and interests of the U.S. Provisional Application 60/472,221 of submission on May 21st, 2003, and whole disclosures of the document are quoted at this as a reference.
Invention field
Present invention relates in general to rapid prototyping design (prototyping) technology, relate more specifically to adopt the three dimensional printing material and the method for thermoplastic granulates shape mixture.
Background
The rapid prototyping designing technique comprises the direct production prototype of the design data goods that produce from computer, a small amount of functional part and be used for the structural ceramics and the ceramic case mould of casting of metals.
Two kinds of known methods that are used for rapid prototyping technology comprise selective laser sintering method and liquid adhesive three dimensional printing method.These technology are similar to a certain extent, all make up three-dimensional article with demixing technology.Two methods form the continuous and thin cross section of desired goods.The adjacent particle that forms independent cross section and be the flat substantially lip-deep granular materials by will being positioned at bed of particulate material is bonded together.On the layer that forms before each layer all is adhered to, thereby when the particle of each layer is bonded together, form desirable three-dimensional article.Laser sintered all favourable with the liquid adhesive technology, because they directly produce parts from the design data that computer produces, and can produce parts with complex geometry configuration.In addition, by " firmly " or " soft " mold making technology machine-building prototype part of routine, when perhaps producing casting or moulding part, according to the complexity of parts, will need the time of several weeks to several months, by comparison, three dimensional printing is faster, and more cheap.
Three dimensional printing has been used to make the ceramic die that is used for model casting, to produce Full Featured casting metals parts.Considered other application of three dimensional printing already.For example, three dimensional printing goes for design-related development, demonstration and mechanical prototype field.It also can be used to produce figure into moulding technology.The three dimensional printing technology can further be used in for example medicine and dentistry field, can make the model of Expected Results before implementation and operation.Other business that can benefit from the rapid prototyping designing technique comprises building constructor, and the design visualization is to its other useful unit.
The selective laser sintering method is described in United States Patent (USP) the 4th, 863, and in No. 568, the full text of the document is quoted at this as a reference.The selective laser sintering method is by the commercialization of DTM company.The selective laser sintering method is included in and sprawls one deck powder thin layer on the plane.Sprawl the instrument that powder is adopted as the development of selective laser sintering method, known in this field is counter-rotating mechanism, or reverse roller (counter-roller).Allow to sprawl the thin layer material relatively equably the layer before can not upsetting with reverse roller.After powder bed is sprawled from the teeth outwards, by predetermined X-Y scheme laser energy is imported powder with laser instrument.Laser makes powder sintered in the laser beam energy impact zone or is melted in together.Powder can be plastics, metal, polymer, pottery or composite.On layer before, form powder bed in succession, then with laser sintered or fusing with reverse roller.This method is hot in essence, need carry enough energy with laser instrument, so that together powder sintered, be sintered on the layer before and the formation end article.
Early stage three dimensional printing technical description is at United States Patent (USP) the 5th, 204, and in 055, the full text of the document is quoted at this as a reference, this technical description use the inkjet type print head, the adhesive material of liquid or colloid is transported on the powder material layer of coating in succession.This three-dimensional ink-jet printing technology or liquid adhesive agent method comprise with reverse roller pulverous material bed being applied on the surface.Powder material is coated onto after surperficial the going up, and ink jet printing head is transported to the liquid adhesive of predetermined pattern on the powder bed.Adhesive infiltrates in the gap of powder material, hardens, and powder material is bonded into the layer of curing.On the layer before the adhesive of sclerosis also is bonded to each layer.Form after first cross-section branch, repeat abovementioned steps, thereby form continuous cross section part, up to forming end article.Optionally, adhesive is suspended in the carrier, and this carrier will evaporate and stay the adhesive of sclerosis.Powder material can be a pottery, metal, and plastics or composite also can comprise fiber.The liquid adhesive material can be an organic or inorganic.The typical organic bond material that uses is a polymer resin, and perhaps ceramic precursor is as polycarbosilazanes (polycarbosilazane).When using inorganic bond, adhesive is contained in the end article; This type of typically uses two silica in using.
An advantage without laser with ink jet printing head can design a plurality of spray nozzles exactly side by side on single print head, so that adhesive is transported on the powder.In the selective laser sintering machine, be the powder conveying capacity only routinely with a laser instrument.Compare with laser sintered, the combination of several spray nozzles is passed through to allow bigger area each to be printed, thereby has increased the speed of liquid adhesive printing.In addition, because laser instrument expensive, and relevant beam deflection optics and control appliance is expensive, and the liquid adhesive printing equipment is than laser equipment considerably cheaper.
At present promptly be used for the powder that selective laser sintering is used for the liquid adhesive technology again, particularly metal dust, have safety problem, this makes them can not be used for office environment ideally.These safety problems may need special clothing and treatment facility, to prevent for example skin contact, perhaps suck noxious material.In addition, in order to meet the toxicant Abgasgesetz, may bring more expense.Owing to these reasons, these technology can not be used for typical office environment, as building and Chevron Research Company (CRC), or doctor's office.
Another kind of three dimensional printing technical description is at United States Patent (USP) the 5th, 902, No. 441 and the 6th, 416, in 850, the full text of these two pieces of documents is quoted at this as a reference, but this technology adopts the mixture of powders that comprises filler and activated adhesive, and can activate the aqueous fluid that this adhesive makes it bonding filler.Fluid apply the employing ink jet printing head.Filler and adhesive can comprise atoxic material separately, as water miscible polymer, and carbohydrate, sugar, sugar alcohol, protein and some organic compound.
This area needs a kind of material system and method, makes it possible to fast, reliable, safety and make outward appearance mould under the office environment inexpensively and the functional part of small batch.Such outward appearance mould and parts need have high-quality surface, accurately limited, and should be tough, non-friable.In addition, some kind mould needs special mechanical performance, as the pliability or the toughness of pressing assembling.
Summary of the invention
The present invention is intended to material system and method, they satisfied to fast, reliable, safety and produce outward appearance mould in the office environment inexpensively and the method demand of small batch functional part.This material system comprises the thermoplastic granulates thing, and it allow to make and accurately to be limited, tough non-friable, outward appearance mould and functional part with smooth surface finish and inessential thin-walled.Thermoplastic is widely used in engineering and consumer products.Therefore, these materials are attractive especially to prototyping technique, because they also can typically be used in the final manufacture method.
On the one hand, the present invention is characterised in that the powder that is suitable for three dimensional printing.This powder comprises the blend of thermoplastic granulates thing and adhesive particle thing, and wherein the adhesive particle thing is suitable for when fluid activates this adhesive particle thing, adhesion heat plastic particle thing.
Can comprise one or more following features.Fluid can be moisture, and is non-moisture, and/or non-halo.The adhesive particle thing can comprise the thermoplastic granulates thing, thus thermoplastic granulates thing slightly soluble and band viscosity at least in activating fluid, and when fluid by being partly dissolved the thermoplastic granulates thing at least, thereby during activation heat plastic particle thing, this thermoplastic granulates thing is suitable for bonding together, and this thermoplastic granulates thing comprises at least a following material: polymethyl methacrylate, polysulfones, polyether sulfone, PPSU, polyacrylonitrile, poly-(acrylonitrile-butadiene-styrene (ABS)), polyamide, melocol condensation polymer, polystyrene, polyolefin, polyvinyl butyral resin, Merlon, polyvinyl chloride, PET, ethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, methylcellulose, cellulose acetate, hydroxypropyl methylcellulose, hydroxy butyl methyl cellulose, HEMC, ethylhydroxyethylcellulose, cellulose xanthate, and their combination and copolymer.
The fluid of activation heat plastic particle thing can be suitable for by being exposed at least a curing the in ultraviolet light, visible light, heat and the electron beam.The thermoplastic granulates thing can comprise the particle of the about 10 μ m of average particulate diameter~about 100 μ m.
The thermoplastic granulates thing can comprise at least a acetal polyformaldehyde, polyactide, polyethylene, polypropylene, ethylene vinyl acetate, polyphenylene oxide, ethylene-acrylic acid copolymer, polyether block amide, polyvinylidene fluoride, polyether-ketone, polybutylene terephthalate, PET, poly terephthalic acid cyclohexylidene methylene ester, polyphenylene sulfide, polythalamide, polymethyl methacrylate, polysulfones, polyether sulfone, PPSU, polyacrylonitrile, poly-(acrylonitrile-butadiene-styrene (ABS)), polyamide, melocol condensation polymer, polystyrene, polyolefin, polyvinyl butyral resin, Merlon, polyvinyl chloride, PET, ethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, methylcellulose, cellulose acetate, hydroxypropyl methylcellulose, hydroxy butyl methyl cellulose, HEMC, ethylhydroxyethylcellulose, cellulose xanthate, and their combination and copolymer.
The adhesive particle thing can comprise the particle of the about 10 μ m of average particulate diameter~about 100 μ m.
Adhesive particle can comprise resin, as water-soluble resin, but or the resin of alkaline reduction (alkaline-reducible), and fluid can activate this adhesive particle thing by the dissolved adhesive particle.Resin can comprise at least a following material: polyvinyl alcohol, the sulfonated polyester polymer, sulfonated polystyrene, the copolymer of octyl acrylamide/acrylate/methacrylic acid fourth amino ethyl ester, the copolymer of acrylate/octyl acrylamide, polyacrylic acid, PVP, the polyacrylic acid of styreneization, PEO, Sodium Polyacrylate, the copolymer of Sodium Polyacrylate and maleic acid, the copolymer of PVP and vinylacetate, butylated PVP, the copolymer of polyvinyl alcohol and vinylacetate, starch, modified starch, cationic starch, the starch of pre-gelatinization, the modified starch of pre-gelatinization, the cationic starch of pre-gelatinization, and their combination and copolymer.
Adhesive can comprise inorganic bond, at least a as following material: gypsum, bentonite, precipitated silicate sodium, unbodied precipitated silica, unbodied precipitated silicate calcium, unbodied precipitated silicate magnesium, unbodied precipitated silicate lithium, salt, portland cement, magnesium phosphate cement, magnesium oxychloride cement contains oxygen magnesium sulfate cement, trbasic zinc phosphate cement, zinc oxide-eugenol cement, aluminium hydroxide, magnesium hydroxide, calcium phosphate, sand, wollastonite, dolomite, contain sodium ion, lithium ion, magnesium ion, with the amorphous sediment silicate of at least two kinds of ions in the calcium ion and their combination.
Powder can comprise filler, and this filler can comprise the particle of the about 5 μ m of average particulate diameter~about 100 μ m.Filler can comprise inorganic material, as aluminium oxide, and soda-lime glass, borosilicate glass, silica, alumino-silicate pottery, lime stone, gypsum, bentonite, precipitated silicate sodium, unbodied precipitated silica, unbodied precipitated silicate calcium, unbodied precipitated silicate magnesium, unbodied precipitated silicate lithium, salt, portland cement, magnesium phosphate cement, magnesium oxychloride cement, contain oxygen magnesium sulfate cement, trbasic zinc phosphate cement, zinc oxide-eugenol cement, aluminium hydroxide, magnesium hydroxide, calcium phosphate, sand, wollastonite, dolomite, contain sodium ion, lithium ion, magnesium ion, with the amorphous sediment silicate of at least two kinds of ions in the calcium ion and their combination.
Filler can comprise organic substance.Organic substance can comprise carbohydrate, as starch, and modified starch, cellulose, maltodextrin, acacia gum, locust bean gum, the starch of pre-gelatinization, the acid modified starch, hydrolyzed starch, sodium carboxymethylcellulose, mosanom, hydroxypropyl cellulose, methylcellulose, chitosan, carrageenan, pectin, agar, gellan gum, Arabic gum, xanthans, propylene glycol alginate, guar gum and their combination.Organic substance can comprise protein, as gelatin, and rabbit skin glue, soybean protein and their combination.
Powder can comprise processing aid, as viscous liquid, and/or low-melting polymer.Processing aid can comprise at least a following material: polyethylene glycol, polypropylene glycol, mono laurate Isosorbide Dinitrate, single oleic acid Isosorbide Dinitrate, three oleic acid Isosorbide Dinitrates, polysorbate, the siloxanes of poly-(ethylene oxide) modification, the siloxanes of poly-(propylene oxide) modification, secondary ethoxylated alcohol, the nonyl phenol of ethoxylation, the octyl phenol of ethoxylation, C
8~C
10Alcohol, C
8~C
10Acid, the acetylenic glycols of poly-(ethylene oxide) modification, citronellol, the siloxanes of ethoxylation, sad second diester, capric acid second diester, 2,4,7,9-tetramethyl-5-decine-4, the ethoxylated derivative of 7-glycol, PEO list oleic acid Isosorbide Dinitrate, polyethylene glycol, soybean oil, mineral oil, the polyethylene oxide polymer of fluoro-alkyl, triacetyl glycerine, oleyl alcohol, oleic acid, squalene, saualane, essential oil, ester, terpenes, grease, or wax, propane diols, ethylene glycol, the C of glycerine
8~C
10Single, double or three esters, aliphatic acid, the aliphatic acid of ethoxylation, lecithin, modified lecithin, tributyrin, stearoyl lactate, the single, double glyceride of diacetyl tartaric acid, corn syrup and their combination.
Powder can comprise fortifying fibre.Fortifying fibre can comprise at least a following material: natural polymer, modified natural polymers, synthetic polymer, pottery, cellulose fibre, silicon carbide fibre, graphite fibre, aluminosilicate fiber, polypropylene fibre, glass fibre, polyamide short fibre, cellulose, artificial silk, polyvinyl alcohol and their combination.
Powder can comprise about 50~100% thermoplastic granulates thing, 0~20% filler, 0~30% adhesive particle thing and 0~2% processing aid.
On the other hand, the present invention is characterised in that the fluid that is used for three dimensional printing, and this fluid comprises first solvent with first boiling point.This fluid is suitable for activating the adhesive in the powder of the blend that comprises thermoplastic granulates thing and adhesive particle thing.
Can comprise one or more following features.Fluid can be suitable for the activated adhesive by the dissolved adhesive particle.First solvent can comprise one or more following materials: ethanol, isopropyl alcohol, normal propyl alcohol, methyl alcohol, n-butanol, glycol, ester, glycol ethers, ketone, aromatic compounds, aliphatic compounds, sprotic polar solvent, terpenes, acrylate, methacrylate, vinyl ethers, oxetanes, epoxide, low-molecular weight polymer, carbonic ester, the N-methyl pyrrolidone, acetone, MEK, dibasic ester, ethyl acetate, dimethyl sulfoxide (DMSO), dimethyl succinate and their combination.
Fluid can comprise second solvent with second boiling point.Second boiling point can be higher than first boiling point, and/or second solvent can be miscible with water.Second solvent can comprise one or more following materials: butyrolactone, carbonic acid glyceride, propylene carbonate, ethylene carbonate, dimethyl succinate, methyl-sulfoxide, N-methyl pyrrolidone, glycerine, 1,4-butanediol, polyethylene glycol, butyl carbitol, ethylene glycol, diethylene glycol (DEG), propane diols, polypropylene glycol, polyglycol ether, polypropylene glycol ether, tetraethylene glycol ether, butylene carbonate, pentanediol, hexylene glycol and their combination.
Fluid can comprise water.First solvent can be miscible with water.Second solvent can be miscible with water.Second solvent can have the second boiling point that is higher than first boiling point.
Fluid can comprise surfactant.Surfactant comprises at least a following material: the acetylenic glycol of PEO modification, secondary ethoxylated alcohol, the nonyl phenol of ethoxylation, the siloxanes of ethoxylation, the fluorinated surfactant of ethoxylation, the tetramethyl decynediol of ethoxylation, the tetramethyl dodecyne glycol of ethoxylation, polyether-modified polysiloxanes, the mono laurate Isosorbide Dinitrate of ethoxylation, Octylphenoxy polyethoxy-poly-propoxyl group-propyl alcohol, alpha-sulfonated fatty acid, zwitterionic betaines, dioctyl sulfonation sodium succinate, dimethyl lauryl propane sulfonic acid ammonium, lauryl sodium sulfate, neopelex, paratoluenesulfonic acid sodium salt, Sodium Benzoate, benzene sulfonic acid sodium salt, potassium sorbate, 2-ethylhexyl sodium sulfonate and their combination.
Fluid can comprise rheology modifiers.The fluid improver can comprise at least a following material: PVP, polyacrylamide, PEO, hydrophobic modified ethyoxyl carbamate, polyvinyl alcohol, polyacrylic acid, polymethylacrylic acid, polyacrylic alkali metal and ammonium salt, the alkali metal of polymethylacrylic acid and ammonium salt, the copolymer of PVP and vinylacetate, butylated PVP, the copolymer of polyvinyl alcohol and vinylacetate, the copolymer of polyacrylic acid and maleic anhydride, sulfonated polystyrene and their combination and copolymer.
Fluid can comprise amine.Amine comprises at least a following material: monoisopropanolamine, triethylamine, 2-amino-2-methyl-1-propanol, 1-amino-2-propyl alcohol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol, N, the N-diethyl ethylene diamine, N methyldiethanol amine, N, the N-dimethylethanolamine, triethanolamine, 2-ethylaminoethanol, two [3-(dimethylamino) propyl group] amino of 1-[]-the 2-propyl alcohol, 3-amino-1-propyl alcohol, 2-(2-aminoethyl amino) ethanol, three (methylol) aminomethane, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, diethanol amine, 1, two (the dimethylamino)-2-propyl alcohol of 3-, ammonium hydroxide, MEA, aminomethyl propanol, aminoethyl ethanolamine, triisopropanolamine, PPOX triamine, polymine and their combination.
On the other hand, the present invention is characterised in that the fluid that is used for three dimensional printing, and this fluid comprises solvent.This fluid is suitable for activating the bond properties of sl. sol. at least thermoplastic granulates thing.
Can comprise one or more following features.This fluid is can right and wrong moisture, and it can be non-halo.Solvent can comprise at least a following material: alcohol, glycol, ester, glycol ethers, ketone, aromatic compounds, aliphatic compounds, sprotic polar solvent, terpenes, acrylate, methacrylate, vinyl ethers, oxetanes, epoxide, low-molecular weight polymer, carbonic ester and their combination.
Alcohol can comprise at least a following material: methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol and their combination.Glycol can comprise at least a following material: ethylene glycol, diethylene glycol (DEG), propane diols, polyethylene glycol, 1,4-butanediol, pentanediol, hexylene glycol and their combination.
Ester can comprise at least a following material: ethyl acetate, acetate propylene glycol monomethyl ether ester, pentyl acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, acetate diethylene glycol monobutyl ether ester, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-butyl acetate, tert-butyl acetate, acetate 2-Octyl Nitrite, oxalic acid second diester, diethyl succinate, methyl lactate, ethyl lactate, dimethyl tartrate, ethyl tartrate and their combination.Glycol ethers can comprise at least a following material: dipropylene glycol methyl ether, diglycol butyl ether, diglycol one ether, propylene glycol monomethyl ether, glycol propyl ether and their combination.
Ketone can comprise at least a following material: acetone, MEK, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl n-pro-pyl ketone, methyl isoamyl ketone, methyl-n-amyl ketone, DIBK and their combination.Aromatic compounds can comprise at least a following material: toluene, dimethylbenzene, phenol, benzene, styrene, aromatic petroleum naphtha of high-flash (naptha) and their combination.
Aliphatic compounds can comprise at least a following material: hexane, heptane, cyclohexane and their combination.Sprotic polar solvent can comprise at least a following material: N-methyl pyrrolidone, methyl-sulfoxide, 2-Pyrrolidone, butyrolactone and their combination.Terpenes can comprise citrene.
Acrylate can comprise at least a following material: oxyalkylated bifunctional acrylate, acrylic acid 2-phenoxy ethyl, tetrahydrofurfuryl acrylate, acrylic acid 2 (2 ethoxy ethoxy) ethyl ester, the own diester of diacrylate, new penta diester of propenoxylated diacrylate, lauryl acrylate, isodecyl acrylate, acrylic acid ester in three last of the ten Heavenly stems, isobornyl acrylate, diacrylate three propylene diesters, acrylic acid octadecane ester, allyl acrylate, Isooctyl acrylate monomer, acrylic acid caprolactone, alkoxylate tetrahydrofurfuryl acrylate, diacrylate fourth diester, diacrylate 1,3-fourth diester, diacrylate diethyl diester, diacrylate is gathered the second diester, the own diester of alkoxylate diacrylate, oxyalkylated diacrylate cyclohexane dimethyl ester, diacrylate cyclohexane dimethyl ester, dipropylene glycol diacrylate, the diacrylate bisphenol-A ester of own oxygen baseization, new penta diester of diacrylate, oxyalkylated aliphatic diacrylate, three acrylic acid trimethyl propyl ester, three (2-hydroxyethyl) isocyanuric acid ester triacrylate, three acrylic acid trimethyl propyl ester of ethoxylation, propenoxylated three acrylic acid trimethyl propyl ester, propenoxylated three acrylic acid glyceride, pentaerythritol tetracrylate, pentaerythritol triacrylate, tetrapropylene acid two trimethyl propyl ester, five acrylic acid dipentaerythritol ester, the pentaerythritol tetracrylate of ethoxylation, oxyalkylated acrylic acid nonyl benzene phenolic ester and their combination.
Methacrylate can comprise at least a following material: methacrylic acid 2-ethyl phenoxy, tetrahydrofurfuryl methacrylate, the own diester of dimethacrylate, lauryl methacrylate, isodecyl methacrylate, methacrylic acid ester in three last of the ten Heavenly stems, isobornyl methacrylate, monomethyl acrylic acid propylene diester, methacrylic acid octadecane ester, allyl methacrylate, EHMA, tetramethylene dimethacrylate, dimethacrylate 1,3-fourth diester, dimethacrylate second diester, dimethacrylate diethyl diester, dimethacrylate three second diester, dimethacrylate tetrem diester, dimethacrylate gathers the second diester, dimethacrylate cyclohexane dimethyl ester, dimethacrylate two propylene diesters, the dimethacrylate bisphenol-A ester of ethoxylation, new penta diester of dimethacrylate, trimethyl acrylic acid trimethyl propyl ester, the methacrylic acid methoxy gathers the second diester, oxyalkylated methacrylic acid nonyl benzene phenolic ester, the hydroxyethyl methacrylate of ethoxylation, allyl methacrylate, propenoxylated allyl methacrylate and their combination.
Vinyl ethers can comprise at least a following material: hydroxy butyl vinyl ether, the triethylene glycol divinyl ether, cyclohexyl dimethanol divinyl ether, the propenyl ether of propylene carbonate, dodecyl vinyl, cyclohexane methanol one vinyl ethers, cyclohexyl vinyl ether, diethylene glycol divinyl ether, 2-ethylhexyl vinyl ethers, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, the hexylene glycol divinyl ether, octadecyl vinyl ether, butanediol divinyl ether, two [4-(ethyleneoxy) butyl] esters of M-phthalic acid, two [4-(ethyleneoxy) butyl] ester and their combinations of adipic acid.
Oxetanes can comprise at least a following material: 3-ethyl-3-methylol-oxetanes, 1, two [(3-ethyl-3-oxa-cyclobutyl methoxy base) methyl] benzene and their combinations of 4-.Epoxide can comprise at least a following material: 3, and 4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate, adipic acid is two-(3, the 4-epoxycyclohexyl) ester, an oxidation citrene, 1,2-epoxy hexadecane and their combination.Low-molecular weight polymer can comprise polymine.Carbonic ester can comprise ethylene carbonate, propylene carbonate, butylene carbonate, carbonic acid glyceride and their combination.
Fluid can comprise water, and solvent can comprise second solvent with second boiling point.Second solvent can comprise at least a following material: butyrolactone, carbonic acid glyceride, propylene carbonate, ethylene carbonate, dimethyl succinate, methyl-sulfoxide, N-methyl pyrrolidone, glycerine, 1,4-butanediol, polyethylene glycol, butyl carbitol, ethylene glycol, diethylene glycol (DEG), propane diols, polypropylene glycol, polyglycol ether, polypropylene glycol ether, tetraethylene glycol ether, butylene carbonate, pentanediol, hexylene glycol and their combination.
Fluid can comprise surfactant.Surfactant comprises at least a following material: the acetylenic glycol of PEO modification, secondary ethoxylated alcohol, the nonyl phenol of ethoxylation, the siloxanes of ethoxylation, the fluorinated surfactant of ethoxylation, tetramethyl decynediol, the tetramethyl decynediol of ethoxylation, the tetramethyl dodecyne glycol of ethoxylation, polyether-modified polysiloxanes, the mono laurate Isosorbide Dinitrate of ethoxylation, Octylphenoxy polyethoxy-poly-propoxyl group-propyl alcohol, alpha-sulfonated fatty acid, zwitterionic betaines, dioctyl sulfonation sodium succinate, dimethyl lauryl propane sulfonic acid ammonium, lauryl sodium sulfate, neopelex, paratoluenesulfonic acid sodium salt, Sodium Benzoate, benzene sulfonic acid sodium salt, potassium sorbate, 2-ethylhexyl sodium sulfonate and their combination.
Fluid can comprise rheology modifiers.The fluid improver can comprise at least a following material: PVP, polyacrylamide, PEO, hydrophobic modified ethyoxyl carbamate, polyvinyl alcohol, polyacrylic acid, polymethylacrylic acid, polyacrylic alkali metal and ammonium salt, the alkali metal of polymethylacrylic acid and ammonium salt, the copolymer of PVP and vinylacetate, butylated PVP, the copolymer of polyvinyl alcohol and vinylacetate, the copolymer of polyacrylic acid and maleic anhydride, sulfonated polystyrene and their combination and copolymer.
Fluid also can comprise first solvent with first boiling point, and this first boiling point is lower than second boiling point.First solvent can comprise at least a following material: ethanol, isopropyl alcohol, normal propyl alcohol, methyl alcohol, n-butanol, glycol, ester, glycol ethers, ketone, aromatic compounds, aliphatic compounds, sprotic polar solvent, terpenes, acrylate, methacrylate, vinyl ethers, oxetanes, epoxide, low-molecular weight polymer, carbonic ester, acetone, ethyl acetate, dimethyl succinate and their combination.
Fluid can comprise amine.Amine comprises at least a following material: monoisopropanolamine, triethylamine, 2-amino-2-methyl-1-propanol, 1-amino-2-propyl alcohol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol, N, the N-diethyl ethylene diamine, N methyldiethanol amine, N, the N-dimethylethanolamine, triethanolamine, 2-ethylaminoethanol, two [3-(dimethylamino) propyl group] amino of 1-[]-the 2-propyl alcohol, 3-amino-1-propyl alcohol, 2-(2-aminoethyl amino) ethanol, three (methylol) aminomethane, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, diethanol amine, 1, two (the dimethylamino)-2-propyl alcohol of 3-, ammonium hydroxide, MEA, aminomethyl propanol, aminoethyl ethanolamine, triisopropanolamine, PPOX triamine, polymine and their combination.
Another aspect, the present invention is characterised in that the fluid that is used for three dimensional printing, this fluid comprises water and amine, but and this fluid be suitable for activating the bond properties of sl. sol. at least alkaline reduction particle.
Can comprise one or more following features.Amine can comprise at least a following material: monoisopropanolamine, triethylamine, 2-amino-2-methyl-1-propanol, 1-amino-2-propyl alcohol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol, N, the N-diethyl ethylene diamine, N methyldiethanol amine, N, the N-dimethylethanolamine, triethanolamine, 2-ethylaminoethanol, two [3-(dimethylamino) propyl group] amino of 1-[]-the 2-propyl alcohol, 3-amino-1-propyl alcohol, 2-(2-aminoethyl amino) ethanol, three (methylol) aminomethane, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, diethanol amine, 1, two (the dimethylamino)-2-propyl alcohol of 3-, ammonium hydroxide, MEA, aminomethyl propanol, aminoethyl ethanolamine, triisopropanolamine, PPOX triamine, polymine and their combination.
Fluid can comprise first solvent with first boiling point.First solvent can comprise at least a following material: ethanol, isopropyl alcohol, normal propyl alcohol, methyl alcohol, n-butanol, glycol, ester, glycol ethers, ketone, aromatic compounds, aliphatic compounds, sprotic polar solvent, terpenes, acrylate, methacrylate, vinyl ethers, oxetanes, epoxide, low-molecular weight polymer, carbonic ester, acetone, ethyl acetate, dimethyl succinate and their combination.
Fluid can comprise second solvent with second boiling point, and wherein second boiling point is higher than first boiling point.Second solvent can comprise at least a following material: butyrolactone, carbonic acid glyceride, propylene carbonate, ethylene carbonate, dimethyl succinate, methyl-sulfoxide, N-methyl pyrrolidone, glycerine, 1,4-butanediol, polyethylene glycol, butyl carbitol, ethylene glycol, diethylene glycol (DEG), propane diols, propane diols, polypropylene glycol, polyglycol ether, polypropylene glycol ether, tetraethylene glycol ether, butylene carbonate, pentanediol, hexylene glycol and their combination.
Fluid can comprise surfactant.Surfactant comprises at least a following material: the acetylenic glycol of PEO modification, secondary ethoxylated alcohol, the nonyl phenol of ethoxylation, the siloxanes of ethoxylation, the fluorinated surfactant of ethoxylation, tetramethyl decynediol, the tetramethyl decynediol of ethoxylation, the tetramethyl dodecyne glycol of ethoxylation, polyether-modified polysiloxanes, the fluorohydrocarbon of ethoxylation, the mono laurate Isosorbide Dinitrate of ethoxylation, Octylphenoxy polyethoxy-poly-propoxyl group-propyl alcohol, alpha-sulfonated fatty acid, zwitterionic betaines, dioctyl sulfonation sodium succinate, dimethyl lauryl propane sulfonic acid ammonium, lauryl sodium sulfate, neopelex, paratoluenesulfonic acid sodium salt, Sodium Benzoate, benzene sulfonic acid sodium salt, potassium sorbate, 2-ethylhexyl sodium sulfonate and their combination.
Fluid can comprise rheology modifiers.The fluid improver can comprise at least a following material: PVP, polyacrylamide, PEO, hydrophobic modified ethyoxyl carbamate, polyvinyl alcohol, polyacrylic acid, polymethylacrylic acid, polyacrylic alkali metal and ammonium salt, the alkali metal of polymethylacrylic acid and ammonium salt, the copolymer of PVP and vinylacetate, butylated PVP, the copolymer of polyvinyl alcohol and vinylacetate, the copolymer of polyacrylic acid and maleic anhydride, sulfonated polystyrene and their combination and copolymer.
On the other hand, the present invention is characterised in that the method that forms goods by three dimensional printing.This method comprises the following steps: to provide a large amount of adjacent particle, and this particle has the average diameter of about 10 μ m~about 100 μ m, and particle comprises the blend of thermoplastic granulates thing and adhesive particle thing; With, fluid is put on these a large amount of particles, wherein the adhesive particle thing is partly soluble at least in this fluid, the thermoplastic granulates thing is basic inertia in this fluid, and this fluid makes the adhesive particle thing activate from the state of basic inertia, the activation amount is enough to these a large amount of particle bond to together, to limit the single goods that are essentially solid.
Can comprise following feature.These goods can be heated, so that this thermoplastic granulates thing of small part sintering.
On the other hand, the present invention is characterised in that the method that forms goods by three dimensional printing.This method comprises the following steps: to provide a large amount of adjacent particle, and this particle has the average diameter of about 10 μ m~about 100 μ m, and particle comprises the blend of thermoplastic granulates thing and adhesive particle thing; With, fluid is put on these a large amount of particles, wherein the adhesive particle thing is partly soluble at least in this fluid, the thermoplastic granulates thing is basic inertia in this fluid, and this fluid dissolved adhesive particle, its meltage is enough to these a large amount of particle bond to together, to limit the single goods that are essentially solid.
Can comprise following feature.These goods can be heated, so that this thermoplastic granulates thing of small part sintering.
On the other hand, the present invention is characterised in that the method that forms goods by three dimensional printing.But this method comprises the following steps: in the first of the first film of the particle that comprises a large amount of thermoplastic granulates and activated adhesive, apply aqueous fluid, this fluid comes activated adhesive with the amount of the single goods that are essentially solid that are enough to form bonded particulate.On the first film, form second film of particle, in the first of second film of the particle of particle, apply aqueous fluid, present in an amount at least sufficient to activated adhesive, make the particle in the first of second film be adhered to one another, and be bonded at least a portion of first of the first film, to form the single goods that are essentially solid from the first of the first film and the first of second film.
Can comprise one or more following features.These goods can heat, so that this thermoplastic granulates thing of small part sintering.
On the other hand, the present invention is characterised in that the method that forms goods by three dimensional printing.This method comprises the following steps: in the first of the first film of the particle that comprises a large amount of thermoplastic granulates, apply non-moisture fluid, this fluid is with the surface of the amount activation heat plastic particle of the single goods that are essentially solid that are enough to form bonded particulate.On the first film, form second film of this particle, in the first of second film of particle, apply this non-aqueous fluid, present in an amount at least sufficient to the surface of activation heat plastic particle, make the particle in the first of second film be adhered to one another, and be bonded at least a portion of first of the first film, to form the single goods that are essentially solid from the first of the first film and the first of second film.On printed layers, apply at least a in ultraviolet light, visible light, heat and the electron beam, solidify to induce non-aqueous fluid.
On the other hand, the present invention is characterised in that a kind of goods, and it comprises the product of following material: powder, this powder contain (i) thermoplastic granulates thing and (ii) adhesive particle thing; And fluid, this fluid activated adhesive particle comprises the goods of the solid basically of powder with formation, and this adhesive particle thing dissolves in this fluid basically.Goods comprise a large amount of adjacent layers that formed by this product, and every layer has the profile that limits the edge and comprises each edge limited goods net shape by these layers.
Can comprise one or more following features.Powder can comprise filler and/or processing aid.Goods can comprise bleeding agent.Bleeding agent can comprise at least a following material: the epoxy-amine system, free radical ultraviolet curing acrylic ester system, cation ultraviolet cured epoxy system comprises the bi-component carbamate system of isocyanates-polyalcohol and isocyanates-amine, cyanoacrylate and their combination.
With reference to following specification and appended claims, these and other feature, aspect and the advantage that the present invention may be better understood.
Summary of drawings
Following accompanying drawing and nonessential drafting in proportion, on the contrary, it focuses on the explanation principle of the invention usually.In conjunction with appended accompanying drawing, read the explanation of following illustrative and embodiment preferred, can understand aforementioned and further feature and advantage of the present invention more fully, and the present invention itself, in the accompanying drawing:
Fig. 1 is the schematic diagram of ground floor of the particle mixture of one embodiment of the invention, shows before any fluid is transferred, and this ground floor is deposited on the surface that can move down of the container of waiting to make up goods.
Fig. 2 is the schematic diagram of inkjet nozzle, and this nozzle is transported to fluid on the part of Fig. 1 layer of particulate matter by predetermined figure.
Fig. 3 is the schematic diagram of the end article of one embodiment of the invention, and these goods are in the container, is made by a plurality of steps shown in Figure 2, and still is immersed in the loose unactivated particle; With
Fig. 4 is the schematic diagram of the end article of Fig. 3.
Detailed Description Of The Invention
The present invention relates to a kind of three dimensional printing material system, this system comprises the thermoplastic granulates filler, adhesive particle thing, and non-essential additional filler, processing aid, fortifying fibre, and/or the mixture of stable fibers; With a kind of fluid, this fluid is suitable for when fluid activated adhesive filler, and adhesion heat plastic particle filler is the goods of solid thereby form substantially. This fluid can be moisture or non-moisture. As used herein, " aqueous fluid " refers to that fluid contains preferred 25% or more, more preferably 40% or more, most preferably 50% or more water. As used herein, " non-aqueous fluid " refers to that fluid contains and is less than 25wt.%, more preferably less than 10wt. %, most preferably be less than the water of 1wt.%. If fluid is non-moisture, then it can comprise the solvent of non-halo. The invention still further relates to the using method of this material system, and the goods produced of the inventive method. The goods that the present invention forms can have excellent accuracy, and remarkable surface smoothness.
As used herein, " thermoplastic granulates thing " attempts to define such filling components: this component bonds when the adhesive particle thing is activated by fluid, it comprise a kind of can because of heating again softening, because of the cooling material of underhardening again. " adhesive " attempts to define such component: this component is erected mechanical bridge between the network component such as particle, and this network component was disperseed before fluid activates, for example the thermoplastic granulates thing. The formation of machinery bridge has caused the formation of solid structure. Adhesive can be water-soluble resin, and fluid can pass through this resin of dissolving and activated adhesive. " resin " attempts to define such material: this material is that minimum molecular weight is the straight or branched of 500 g/mols organic chemistry subunit. In certain embodiments, adhesive comprises thermoplastic itself. " filler " attempts to define such component: this component was solid before applying the activation fluid, the specific viscosity mixture is dissolved in this fluid significantly less, and this component is given the final product structure globality. Can adopt the filler except thermoplastic, for example various inorganic or organic substances. The mechanical bridge that " bonding " attempt to define between the discrete particles thing, be used to form network makes up.
Granulate mixture can comprise fortifying fibre or fortifying fibre matter component, and their adding can be end article structural reinforcing is provided. As used herein, " fiber " or " cellulosic component " attempts to define such component: this component is solid before activating fluid applying, can be advantageously but optionally be insoluble in this fluid. Can add fiber or cellulosic component, to strengthen the intensity of end article. In certain embodiments, stable fibers can be added in the filler, for end article provides dimensional stability, thereby the body powder is passed in the migration of control liquid, and slightly increases product strength.
Fiber is solid constituent, and the average length of its main texture (primary grains) is grown to than the averga cross section size and lacked 3~4 times. Materials is common by industry. For the three dimensional printing purpose, fiber is usually useful in the finite size scope, and this scope is the thickness that about powder is sprawled layer, and is perhaps less.
In some embodiment, can add the processing aid compound in the granulate mixture, as serve as the viscous liquid that prints auxiliary agent, the twisted phenomena when preventing from printing or make it to minimize. The fine particle of mixture was spread out in the air when processing aid can prevent the print head dispense liquid, and the latter will make goods distortion to be printed, thereby depart from ideal configuration.
With reference to figure 1, according to the printing process that utilizes material system of the present invention, container 24 can linear translational surface 22 on the layer or the film of coated particle thing 20.The layer of particle 20 or the formation of film can be adopted any suitable mode, for example utilize reverse roller.Be coated on lip-deep particle 20 and comprise thermoplastic granulates filler and adhesive particle thing.Particle 20 also can comprise additional filler, processing aid, and/or fibrous material.
With reference to figure 2, inkjet type nozzle 28 is pressed the mode of X-Y scheme, will activate at least a portion 30 that fluid 26 is transported to the layer of granulate mixture 20 or film.According to this printing process, can (be circular in the figure by any predetermined X-Y scheme, only be illustrative purposes) fluid 26 is transported on the layer or film of particle 20, this can utilize any mechanism easily, for example, can use drop on demand ink jet (DOD) print head, this print head is by the software-driven of the goods model data of foundation CAD (CAD) system.
The first 30 of granulate mixture is activated by fluid 26, makes the particle bond be activated together, and forming substantially is the circular layer of solid, and this layer becomes the cross section part (for example referring to Fig. 3 and 4) of end article 38.As used herein, " activation " attempt the definition from basic inertia to adhesive state variation.This definition comprises the activated adhesive particle with adhesion heat plastic particle thing, and/or heat of solution plastic particle thing at least in part.When fluid contacted granulate mixture at first, because capillarity, fluid outwards flowed (on the microcosmic degree) from shock point immediately, thereby in short relatively time such as initial several seconds, dissolved adhesive and/or thermoplastic granulates thing.The typical fluid drop that activates has the about 100 husky volumes that rise (pl), behind the contact granulate mixture, is extended to the about 100 μ m of diameter.Because dissolution with solvents adhesive, the viscosity of fluid significantly increases, and has stoped the further migration of fluid from initial impact point.Within several minutes, the fluid that has dissolved adhesive infiltrates in lower and particle porous slightly of dissolubility, between the thermoplastic granulates thing, and forms adhesive bond between additional filler and the fiber.The granulate mixture amount that the activation fluid can be bonded together is the several times of fluid drop quality.Along with the evaporation of the volatile component of fluid, so the adhesive bond sclerosis, thereby with thermoplastic granulates thing and non-essential additional filler, and the fiber grain thing connects into the structure of rigidity, becomes the cross section part of end article 38.
But any un-activation granulate mixture 32 that is not exposed to fluid keeps loose and free-flowing on movable surface 22.Typically, unactivated granulate mixture will be stayed original position always, up to the moulding of finishing end article 38.Unactivated loose particles mixture is stayed original position, guaranteed that goods 38 are fully supported in process, thus allow to limit and form such as overhang, the feature in undercutting (undercut) and hole, and need not to adopt the supplementary support structure.In this embodiment, after first cross-section that forms end article 38 is divided, movable surface 22 is replaced downwards, and repeat this method.
Then, for example reverse roller of usefulness mechanism, second film of coated particle mixture or layer on ground floor make it cover the first cross section part and any approaching loose particles mixture of rigidity.The fluid of coating flows in foregoing mode for the second time, and dissolved adhesive, between at least a portion of aforementioned cross section moulding section, the thermoplastic granulates thing of the second layer, non-essential filler and fiber, form adhesive bond, and sclerosis, to form the second rigidity cross section part, the latter is added on the first rigidity cross section part of end article.Once more movable surface 22 is replaced downwards.
Repeat abovementioned steps, i.e. coating contains the granulate mixture layer of adhesive, and coating activates fluid and movable surface 22 is replaced downwards, up to finishing end article 38.With reference to figure 3, end article 38 can be an Any shape, and is for example cylindrical.When method finishes, the end face 34 of visible end article 38 only in the container 24.Typically, end article 38 is submerged in the outer bed 36 of un-activation particle fully.In addition, level and smooth and print a series of this type of layers by depositing, make it successively, can upwards form the goods of multilayer from immovable platform.
With reference to figure 4, can from final cylindrical product 38, remove unactivated particle by forced air stream or vacuum.From goods 38, remove after the un-activation particle, can carry out back processing and handle, for example infiltration of cleaning, stabilizing material and japanning etc.The suitable bleeding agent that is used to stablize this material can be selected from for example epoxy-amine system, free radical ultra-violet curing acrylatcs systems, the outer cured epoxy system of cationic violet, the bi-component carbamate system that comprises isocyanates-polyalcohol and isocyanates-amine, cyanoacrylate and their combination.Post processing also can comprise heating product, so that small part sintering thermoplastic granulates thing.Sintering for example can be finished down at 110 ℃ in about 45 minutes, and this depends on the composition of end article 38.
The feature that method of the present invention can produce comprises about 250 microns (μ m) or higher size.The accuracy that the inventive method obtained is about ± 250 μ m.The amount of contraction of end article 38 is about 1%, can decompose at an easy rate in the member, to increase accuracy.The quality height of surface smoothness, porosity is about 50%, the about 200 μ m of surface roughness.End article 38 can have the thin-walled of thickness for example about 1 millimeter (mm).
Powder constituent
The thermoplastic granulates filler
The thermoplastic granulates filler is the key component of material system of the present invention.This particle can comprise any thermoplastic of the about 10 μ m of average grain diameter~about 100 μ m, yet this extraneous size also can be considered.
Suitably some examples of thermoplastic powder material are:
1) acetal polyformaldehyde;
2) polyactide;
3) polyethylene;
4) polypropylene;
5) ethylene vinyl acetate;
6) polyphenylene oxide;
7) ethylene-acrylic acid copolymer;
8) polyether block amide;
9) polyvinylidene fluoride;
10) polyether-ketone;
11) polybutylene terephthalate;
12) PET;
13) poly terephthalic acid cyclohexylidene methylene ester;
14) polyphenylene sulfide;
15)polythalamide;
16) polymethyl methacrylate;
17) polysulfones;
18) polyether sulfone;
19) PPSU;
20) polyacrylonitrile;
21) poly-(acrylonitrile-butadiene-styrene (ABS));
22) polyamide;
23) melocol condensation polymer;
24) polystyrene;
25) polyolefin;
26) polyvinyl butyral resin;
27) Merlon;
28) polyvinyl chloride;
29) PET;
30) cellulose family comprises ethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, methylcellulose, cellulose acetate, hydroxypropyl methylcellulose, hydroxy butyl methyl cellulose, HEMC, ethylhydroxyethylcellulose, cellulose xanthate; With
Their combination and copolymer.
Adhesive
The adhesive particle thing is the compound of choosing, and makes it have following one or more performances: high-dissolvability, low solution viscosity, low water absorbable and high bonding strength in activating fluid.Adhesive preferably can highly be dissolved in the activation fluid, can fully be combined in the fluid fast and substantially to guarantee it.With before thermoplastic granulates filler and/or filler particle mix; the fine gtinding adhesive; to increase available surface area; thereby be increased in the dissolving in the fluid; but can not be meticulous so that produce " caking "; " caking " is a kind of unfavorable goods feature, and the powder that wherein is not activated additionally is bonded on the member outer surface, thereby causes the surperficial definition of difference.Typical adhesive particle diameter is about 10 μ m~about 100 μ m.The low water absorbable of adhesive avoids absorbing excess humidity from air, moisture also is one of reason of undesirable caking.
In some embodiment, adhesive of the present invention is water miscible, and promptly adhesive is dissolved in aqueous fluid.The compound that is suitable for use as adhesive of the present invention can be selected from following non-limiting group: water-soluble polymer, but the resin of alkaline reduction, carbohydrate, sugar, sugar alcohol, protein and some inorganic compound.In some embodiment, preferred low-molecular-weight water-soluble polymer, because they can dissolve quickly, this is diffused in the solution quickly owing to less molecular energy.Suitable water-soluble resin comprises:
1) polyvinyl alcohol;
2) sulfonated polyester polymer;
3) sulfonated polystyrene;
4) copolymer of octyl acrylamide/acrylate/methacrylic acid fourth amino ethyl ester;
5) copolymer of acrylate/octyl acrylamide;
6) polyacrylic acid;
7) PVP;
8) polyacrylic acid of styreneization;
9) PEO;
10) Sodium Polyacrylate;
11) copolymer of Sodium Polyacrylate and maleic acid;
12) copolymer of PVP and vinylacetate;
13) butylated PVP; With
14) copolymer of polyvinyl alcohol and vinylacetate;
15) starch;
16) modified starch;
17) cationic starch;
18) starch of pre-gelatinization;
19) modified starch of pre-gelatinization;
20) cationic starch of pre-gelatinization;
And their combination and copolymer.
Adhesive can comprise carbohydrate, as starch, and cellulose, maltodextrin, acacia gum, locust bean gum, the starch of pre-gelatinization, sour modified starch, hydrolyzed starch, sodium carboxymethylcellulose, mosanom, hydroxypropyl cellulose, chitosan, carrageenan, pectin, agar, gellan gum, Arabic gum, xanthans, propylene glycol alginate, guar gum and their combination.Suitable sugar and sugar alcohol comprise sucrose, glucose, fructose, lactose, polydextrose, sorbierite, xylitol, ring glucan and their combination.Also can adopt to comprise the organic acid organic compound, comprise citric acid, butanedioic acid, polyacrylic acid urea and their combination.Organic compound also can comprise protein, as gelatin, and rabbit skin glue, soybean protein and their combination.Inorganic compound comprises gypsum, bentonite, precipitated silicate sodium, unbodied precipitated silica, unbodied precipitated silicate calcium, unbodied precipitated silicate magnesium, unbodied precipitated silicate lithium, two or more the amorphous sediment silicate of combination that contains sodium ion, lithium ion, magnesium ion and calcium ion, salt, portland cement, magnesium phosphate cement, magnesium oxychloride cement contains oxygen magnesium sulfate cement, trbasic zinc phosphate cement, zinc oxide-eugenol cement, aluminium hydroxide, magnesium hydroxide, calcium phosphate, husky, wollastonite, dolomite and their combination.
Thermoplastic as adhesive
In some embodiment, do not need independent component to serve as adhesive.The thermoplastic granulates thing can print together with fluid, and wherein the thermoplastic granulates thing is slightly soluble in this fluid at least.The thermoplastic granulates thing example that can serve as adhesive comprises:
1) acetal polyformaldehyde;
2) polyactide;
3) polyethylene;
4) polypropylene;
5) ethylene vinyl acetate;
6) polyphenylene oxide;
7) ethene and acrylic acid copolymer;
8) polyether block amide;
9) polyvinylidene fluoride;
10) polyether-ketone;
11) polybutylene terephthalate;
12) PET;
13) poly terephthalic acid cyclohexylidene methylene ester;
14) polyphenylene sulfide;
15)polythalamide;
16) polymethyl methacrylate;
17) polysulfones;
18) polyether sulfone;
19) PPSU;
20) polyacrylonitrile;
21) poly-(acrylonitrile-butadiene-styrene (ABS));
22) polyamide;
23) condensation polymer of melocol;
24) polystyrene;
25) polyolefin;
26) polyvinyl butyral resin;
27) Merlon;
28) polyvinyl chloride;
29) PET; With
30) cellulose family comprises ethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, methylcellulose, cellulose acetate, hydroxypropyl methylcellulose, hydroxy butyl methyl cellulose, HEMC, ethylhydroxyethylcellulose, cellulose xanthate; With
Their combination and copolymer.
Filler
Additional filler of the present invention is different from the thermoplastic granulates filler, and it is the compound of choosing, and makes it have not dissolving or the feature of utmost point low-solubility, quick humidification, low water absorbable and high bonding strength in activating fluid.This filler provides frame for movement for hardening composition.Sl. sol. filler is normally favourable, but also can use insoluble filler.This filler particle apply activate fluid after during adhesive drying/sclerosis, be bonded together.The practical minimum diameter of the scope that filler typically comprises particle size distribution from the actual maximum gauge of about 100 μ m to about 5 μ m.By in powder, forming macropore, fluid can be moved rapidly pass through, as if big particle size can be improved the quality of end article, thereby allows to produce the more material of homogeneous.The smaller particles size is used to strengthen the intensity of goods.Therefore, the distribution of particle size provides the advantage of the two.
The compound that is suitable for use as filler of the present invention can be selected from various general groups, as long as they can satisfy the standard of aforementioned dissolubility, water imbibition, bonding strength and solution viscosity.Filler can be inorganic, aluminium oxide for example, soda-lime glass, borosilicate glass, silica, aluminosilicate pottery, lime stone, gypsum, bentonite, precipitated silicate sodium, unbodied precipitated silica, unbodied precipitated silicate calcium, unbodied precipitated silicate magnesium, unbodied precipitated silicate lithium contains sodium ion, lithium ion, magnesium ion, two or more the amorphous sediment silicate of combination with calcium ion, salt, portland cement, magnesium phosphate cement, magnesium oxychloride cement contains oxygen magnesium sulfate cement, trbasic zinc phosphate cement, zinc oxide-eugenol cement, aluminium hydroxide, magnesium hydroxide, calcium phosphate, sand, wollastonite, dolomite and their combination.In addition, filler can be organically, carbohydrate for example, and as starch, starch derivatives, cellulose, maltodextrin and their combination.Usually, which kind of filler is choice of Solvent determined to use.Apply activate fluid before, filler is a solid, through selecting so that the solubility of filler in fluid significantly less than the solubility of adhesive in this fluid.
Advantageously, the powder constituent that contains filler has high absorbent properties, thereby can absorb and keep bleeding agent.
Fiber
In some embodiment, granulate mixture can comprise fortifying fibre or fortifying fibre matter component, and their end article that is incorporated as provides structure to strengthen and structural integrity.Particle can comprise that a lot of average diameters are the particle of about 10~100 μ m.The length of fortifying fibre is restricted to the length that approximates the granulate mixture layer thickness usually.It is long that fortifying fibre length typically is about 60 μ m~about 200 μ m, and its content is that being no more than of total mixture is about 50%, preferably is no more than 30%, is most preferably not exceeding about 20%.
Fortifying fibre of the present invention preferably is insoluble to the fluid of activated adhesive, and perhaps the specific viscosity mixture is dissolved in this fluid significantly slowlyer.Fortifying fibre can be chosen firm relatively material, strengthens and size Control with the machinery that increases end article, can not make powder be difficult to sprawl simultaneously.In order to promote the wetability of fortifying fibre, selected fiber can advantageously have the relative high-affinity to solvent.In one embodiment, fibre length approximates layer thickness, and this provides the machinery of significance degree to strengthen.Adopt long fiber to be tending towards surface smoothness is had a negative impact, and adopt the feasible powder difficulty more of sprawling of fiber of too much random length.Be suitable for strengthening fibrous material of the present invention and include but not limited to cellulose, polymer fiber, ceramic fibre, graphite fibre, glass fibre and their combination.Polymer fiber can be cellulose and cellulose derivative, or contains the replacement of maximum 8 carbon atoms or the monomer of unsubstituted, straight or branched, alkyl or alkene.Concrete usable fibers material includes but not limited to natural polymer, modified natural polymers, synthetic polymer, pottery, cellulose fibre, silicon carbide fibre, graphite fibre, aluminosilicate fiber, polypropylene fibre, glass fibre, polyamide short fibre, cellulose, artificial silk, polyvinyl alcohol and their combination.
In some embodiment, can in filler, add stable fibers,, also increase the intensity of goods slightly for end article provides dimensional stability.When the frictional force that causes when stable fibers in the mixture is excessive increases, sprawl granulate mixture with reverse roller and become difficult more, reduced packed density.Therefore, the restriction of stable fibers quantity and length has been increased the packed density of this mixture, thereby produced final parts with greater strength.Usually, stable fibers is restricted to the only about half of length that is less than fortifying fibre, quantity is no more than the 50wt.% of total mixture, preferably is no more than 40wt.%, is most preferably not exceeding about 30wt.%.Optimum value can be determined by conventional experiment with for example reverse roller.
Fortifying fibre and stable fibers can be celluloses.Cellulosic some useful performance makes it be particularly suitable for using in conjunction with the present invention, and this performance is the easily acquired of hypotoxicity, biodegradability, low cost and extensive length range.
Further consider the ideal performance that depends on end article when selecting thermoplastic granulates thing, adhesive, filler and fiber.The non-adhesive contact quality that does not rely on significantly between the compound particles of the final strength of the goods of finishing, and the emptying aperture size that leaves in the material of adhesive sclerosis back; These two kinds of factors are along with the particle size of particle changes.Usually, the particle mean size of particle preferably is not more than bed thickness.The distribution of particle size has increased the packed density of particle, and this has increased product strength and size Control conversely again.
Processing aid
The processing aid that is used for three dimensional printing is the viscous liquid component of powder material system typically.It can be a liquid polymers, or has low-melting polymer.Preferably, it is non-moisture, therefore not with the water-soluble powder component reaction.By combining powder loosely, processing aid makes multilayer can not move when sprawling.Processing aid also serves as wetting agent, attracts fluid and allows fluid to sprawl fast.In addition, processing aid can reduce dust formation.The examples of materials that can be used as processing aid comprises polyethylene glycol, polypropylene glycol (PPG), mono laurate Isosorbide Dinitrate, single oleic acid Isosorbide Dinitrate, three oleic acid Isosorbide Dinitrates, polysorbate, the siloxanes of poly-(ethylene oxide) modification, the siloxanes of poly-(propylene oxide) modification, secondary ethoxylated alcohol, the nonyl phenol of ethoxylation, the octyl phenol of ethoxylation, C
8~C
10Alcohol, C
8~C
10Acid, the acetylenic glycols of poly-(ethylene oxide) modification, citronellol, the siloxanes of ethoxylation, sad second diester, capric acid second diester, 2,4,7,9-tetramethyl-5-decine-4, the ethoxylated derivative of 7-glycol, PEO list oleic acid Isosorbide Dinitrate, soybean oil, mineral oil, the polyethylene oxide polymer of fluoro-alkyl, triacetyl glycerine, oleyl alcohol, oleic acid, squalene, saualane, essential oil, ester, terpenes, grease, wax, propane diols, ethylene glycol, the C of glycerine
8~C
10Single, double or three esters, aliphatic acid, the aliphatic acid of ethoxylation, lecithin, modified lecithin, tributyrin, stearoyl lactate, the single, double glyceride of diacetyl tartaric acid, corn syrup and their combination.
Activate fluid
Select fluid of the present invention, make it to be complementary with the required above-mentioned dissolubility degree of the various particle components of mixture.In case low relatively solution viscosity guarantees that adhesive is dissolved in and activates in the fluid, fluid can fast transferring position in the powder bed, thermoplasticity filler and enhancing substance are bonded together.Fluid can be moisture or non-moisture.Aqueous fluid moisture preferred 25% or more, more preferably 40% or more, most preferably 50% or more.The moisture 25wt.% that is less than of non-aqueous fluid more preferably less than 10wt.%, most preferably is less than 1wt.%.
First solvent
Fluid can comprise first solvent with first boiling point, and adhesive has activity in this first solvent, and preferably dissolves in this solvent.First solvent can be suitable for the activated adhesive by the dissolved adhesive particle, also is suitable for helping the dissolving of fluid.First solvent can be non-hydrous matter, ethanol, isopropyl alcohol, normal propyl alcohol, methyl alcohol, n-butanol, glycol, ester, glycol ethers, ketone, aromatic compounds, aliphatic compounds, sprotic polar solvent, terpenes, acrylate, methacrylate, vinyl ethers, oxetanes, epoxide, low-molecular weight polymer, carbonic ester, N-methyl pyrrolidone, acetone, MEK, dibasic ester, ethyl acetate, dimethyl sulfoxide (DMSO), dimethyl succinate and their combination.Have high boiling appropriate solvent and be suitable for dissolving some thermoplastic, when dissolution with solvents thermoplastic granulates is bonded together, the example of this solvent is:
1) N-methyl pyrrolidone, acetone, MEK, dibasic ester and vinylacetate can be used for dissolving polymethyl methacrylate;
2) methyl-sulfoxide, N-methyl pyrrolidone and acetone can be used for dissolving polysulfones, polyether sulfone and PPSU; With
3) methyl-sulfoxide, N-methyl pyrrolidone and acetone can be used for dissolving polyacrylonitrile.
Second solvent (wetting agent)
Can contain second solvent (wetting agent) in the fluid, it has the second boiling point that possibility is higher than first boiling point, is used for stoping the material of fluid after the printing to evaporate away, and prevents the drying/obstruction of print head induction system.This second solvent can be miscible with water, can comprise for example butyrolactone, carbonic acid glyceride, propylene carbonate, ethylene carbonate, dimethyl succinate, methyl-sulfoxide, N-methyl pyrrolidone, glycerine, 1,4-butanediol, polyethylene glycol, butyl carbitol, ethylene glycol, diethylene glycol (DEG), propane diols, polypropylene glycol, polyglycol ether, polypropylene glycol ether, tetraethylene glycol ether, butylene carbonate, pentanediol, hexylene glycol and their combination.
Surfactant
Can add surfactant in the described fluid,, thereby help it to skid off the nozzle of print head with the surface tension of minimizing fluid.Surfactant can be the acetylenic glycol of PEO modification for example, secondary ethoxylated alcohol, the nonyl phenol of ethoxylation, the siloxanes of ethoxylation, the fluorinated surfactant of ethoxylation, tetramethyl decynediol, the tetramethyl decynediol of ethoxylation, the tetramethyl dodecyne glycol of ethoxylation, polyether-modified polysiloxanes, the mono laurate Isosorbide Dinitrate of ethoxylation, Octylphenoxy polyethoxy-poly-propoxyl group-propyl alcohol, alpha-sulfonated fatty acid, zwitterionic betaines, dioctyl sulfonation sodium succinate, dimethyl lauryl propane sulfonic acid ammonium, lauryl sodium sulfate, neopelex, paratoluenesulfonic acid sodium salt, Sodium Benzoate, benzene sulfonic acid sodium salt, potassium sorbate, 2-ethylhexyl sodium sulfonate and their combination.
Rheology modifiers
Can add rheology modifiers in the described fluid with increase viscosity, thereby increase the efficient of print head and help printing.Possible rheology modifiers example comprises PVP, polyacrylamide, PEO, hydrophobic modified ethyoxyl carbamate, polyvinyl alcohol, polyacrylic acid, polymethylacrylic acid, polyacrylic alkali metal and ammonium salt, the alkali metal of polymethylacrylic acid and ammonium salt, the copolymer of PVP and vinylacetate, butylated PVP, the copolymer of polyvinyl alcohol and vinylacetate, the copolymer of polyacrylic acid and maleic anhydride, sulfonated polystyrene and their combination and copolymer.
Amine
Can add amine in the described fluid, with the resin of assist in dissolving and mixable adhesive of water such as water soluble.The example of suitable amine comprises monoisopropanolamine, triethylamine, 2-amino-2-methyl-1-propanol, 1-amino-2-propyl alcohol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol, N, the N-diethyl ethylene diamine, N methyldiethanol amine, N, the N-dimethylethanolamine, triethanolamine, 2-ethylaminoethanol, two [3-(dimethylamino) propyl group] amino of 1-[]-the 2-propyl alcohol, 3-amino-1-propyl alcohol, 2-(2-aminoethyl amino) ethanol, three (methylol) aminomethane, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, diethanol amine, 1, two (the dimethylamino)-2-propyl alcohol of 3-, ammonium hydroxide, MEA, aminomethyl propanol, aminoethyl ethanolamine, triisopropanolamine, PPOX triamine, polymine and their combination.
Be used to activate the fluid of sl. sol. thermoplastic granulates thing
Some activates fluid and is suitable for activating the bond properties of slightly soluble thermoplastic granulates thing at least.Such activation fluid has softened the surface of solid particle, thereby makes that this surface can self be bonding.These fluids are the fluid of moisture, the non-halo of right and wrong typically, as alcohol, and glycol, ester, glycol ethers, ketone, aromatic compounds, aliphatic compounds, sprotic polar solvent, terpenes, acrylate, methacrylate, vinyl ethers, oxetanes, epoxide, low-molecular weight polymer, carbonic ester and their combination.Activating fluid as some of the solvent of thermoplastic granulates thing can be after the heat of solution ductile material, by being exposed to ultraviolet light, visible light, heat or electron beam or their combination is cured.
Alcohol can comprise at least a following material: methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol and their combination.Glycol can comprise at least a following material: ethylene glycol, diethylene glycol (DEG), propane diols, polyethylene glycol, butanediol, pentanediol, hexylene glycol and their combination.
Ester can comprise at least a following material: ethyl acetate, acetate propylene glycol monomethyl ether ester, pentyl acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, acetate DEGMBE ester, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-butyl acetate, tert-butyl acetate, acetate 2-Octyl Nitrite, oxalic acid second diester, diethyl succinate, methyl lactate, ethyl lactate, dimethyl tartrate, ethyl tartrate and their combination.Glycol ethers can comprise at least a following material: dipropylene glycol methyl ether, diglycol butyl ether, diglycol one ether, propylene glycol monomethyl ether, glycol propyl ether and their combination.
Ketone can comprise at least a following material: acetone, MEK, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl n-pro-pyl ketone, methyl isoamyl ketone, methyl-n-amyl ketone, DIBK and their combination.Aromatic compounds can comprise at least a following material: toluene, dimethylbenzene, phenol, benzene, styrene, the aromatic petroleum naphtha of high-flash and their combination.
Aliphatic compounds can comprise at least a following material: hexane, heptane, cyclohexane and their combination.Sprotic polar solvent can comprise at least a following material: N-methyl pyrrolidone, methyl-sulfoxide, 2-Pyrrolidone, butyrolactone and their combination.Terpenes can comprise citrene.
Acrylate can comprise at least a following material: oxyalkylated bifunctional acrylate, acrylic acid 2-phenoxy ethyl, tetrahydrofurfuryl acrylate, acrylic acid 2 (2 ethoxy ethoxy) ethyl ester, the own diester of diacrylate, new penta diester of propenoxylated diacrylate, lauryl acrylate, isodecyl acrylate, acrylic acid ester in three last of the ten Heavenly stems, isobornyl acrylate, diacrylate three propylene diesters, acrylic acid octadecane ester, allyl acrylate, Isooctyl acrylate monomer, the acrylic acid caprolactone, alkoxylate tetrahydrofurfuryl acrylate, diacrylate fourth diester, diacrylate 1,3-fourth diester, diacrylate diethyl diester, diacrylate is gathered the second diester, the own diester of alkoxylate diacrylate, oxyalkylated diacrylate cyclohexane dimethyl ester, diacrylate cyclohexane dimethyl ester, dipropylene glycol diacrylate, the diacrylate bisphenol-A ester of ethoxylation, new penta diester of diacrylate, oxyalkylated aliphatic diacrylate, three acrylic acid trimethyl propyl ester, three (2-hydroxyethyl) isocyanuric acid ester triacrylate, three acrylic acid trimethyl propyl ester of ethoxylation, propenoxylated three acrylic acid trimethyl propyl ester, propenoxylated three acrylic acid glyceride, pentaerythritol tetracrylate, pentaerythritol triacrylate, tetrapropylene acid two trimethyl propyl ester, five acrylic acid dipentaerythritol ester, the pentaerythritol tetracrylate of ethoxylation, oxyalkylated acrylic acid nonyl benzene phenolic ester and their combination.
Methacrylate can comprise at least a following material: methacrylic acid 2-ethyl phenoxy, tetrahydrofurfuryl methacrylate, the own diester of dimethacrylate, lauryl methacrylate, isodecyl methacrylate, methacrylic acid ester in three last of the ten Heavenly stems, isobornyl methacrylate, monomethyl acrylic acid propylene diester, methacrylic acid octadecane ester, allyl methacrylate, EHMA, tetramethylene dimethacrylate, dimethacrylate 1,3-fourth diester, dimethacrylate second diester, dimethacrylate diethyl diester, dimethacrylate three second diester, dimethacrylate tetrem diester, dimethacrylate gathers the second diester, dimethacrylate cyclohexane dimethyl ester, dimethacrylate two propylene diesters, the dimethacrylate bisphenol-A ester of ethoxylation, new penta diester of dimethacrylate, trimethyl acrylic acid trimethyl propyl ester, the methacrylic acid methoxy gathers the second diester, oxyalkylated methacrylic acid nonyl benzene phenolic ester, the hydroxyethyl methacrylate of ethoxylation, allyl methacrylate, propenoxylated allyl methacrylate and their combination.
Vinyl ethers can comprise at least a following material: hydroxy butyl vinyl ether, the triethylene glycol divinyl ether, cyclohexyl dimethanol divinyl ether, the propenyl ether of propylene carbonate, dodecyl vinyl, cyclohexane methanol one vinyl ethers, cyclohexyl vinyl ether, diethylene glycol divinyl ether, 2-ethylhexyl vinyl ethers, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, the hexylene glycol divinyl ether, octadecyl vinyl ether, butanediol divinyl ether, two [4-(ethyleneoxy) butyl] esters of M-phthalic acid, two [4-(ethyleneoxy) butyl] ester and their combinations of adipic acid.
Oxetanes can comprise at least a following material: 3-ethyl-3-methylol-oxetanes, 1, two [(3-ethyl-3-oxa-cyclobutyl methoxy base) methyl] benzene and their combinations of 4-.Epoxide can comprise at least a following material: 3, and 4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate, adipic acid is two-(3, the 4-epoxycyclohexyl) ester, an oxidation citrene, 1,2-epoxy hexadecane and their combination.Low-molecular weight polymer can comprise polymine.Carbonic ester can comprise ethylene carbonate, propylene carbonate, butylene carbonate, carbonic acid glyceride and their combination.
In these activation fluids some is reactive monomer, serves as the solvent of thermoplastic granulates thing.The first step, activating fluid can the heat of solution ductile material, and infiltrates this thermoplastic.This behavior can be promoted by the activation fluid of selecting to contain monomer, the Hansen solubility parameter of this monomer and the Hansen solubility parameter of thermoplastic granulates thing coupling.The Hansen solubility parameter is a quantitative values, and it describes the solvability behavior of fluid and the solubility characteristics of thermoplastic.Second step, can cause mechanism, cation initiation mechanism or the combination of the two by free radical, further solidify the monomer that activates fluid.Fluid such as acrylate, methacrylate, vinyl ethers, oxetanes, epoxide and combination thereof is typical reactive monomer, and it also can serve as solvent.Serve as solvent, and when dissolution with solvents, be suitable for dissolving some thermoplastic, and infiltrate in the thermoplastic granulates so that the example of the monomer that thermoplastic granulates bonds together is:
1) the own diester of diacrylate---solubilized Merlon, polystyrene and PET.
2) hexylene glycol divinyl ether---solubilized polystyrene.
3) diglycidyl ether of bisphenol-A---dissolvable agents polysulfones or polyether sulfone.
The monomer dissolving is also infiltrated after the thermoplastic granulates thing, (monomer belongs to acrylate by the free radical initiation subsequently, methacrylate, or under the situation of vinyl compound family), cation causes (monomer belongs under the situation of epoxide and oxetanes family) and makes it to solidify.The monomer of vinyl ethers family can cause by free radical or cation and solidify.The monomer that infiltrates in the thermoplastic granulates thing is solidified produce interpenetrating polymer networks (IPN).IPN is meant the polymer network of two or more components, their polymerizations and/or crosslinked in the presence of vicinity each other.Preferably, such polymerization system comprises two or more network polymers, and they infiltrate each other mutually on a certain degree, connect but not chemical bonding, thereby unless break chemical bond, otherwise can not separate them.Between the monomer of thermoplastic granulates thing and polymerization, form IPN and make it possible to bond better, and the enhancing toughness of end article is provided.
Table 1 provides the summary of one group of preferred feed, and this material is used to comprise the granulate mixture of thermoplastic and adhesive, and is used to activate fluid.Table 2 provides the summary of two preferred feed embodiment, the thermoplastic that this material bonds together when being used to be adapted at the contact activation fluid, and be used to activate fluid.
Table 1
Component | Preferred compound | Acceptable compositing range (wt.%) | Preferred form (wt.%) | Particle size range (μ m) |
Granulate mixture | ||||
Thermoplastic | Polymethyl methacrylate | 50~100% | 74.4 | 10~100 |
Adhesive | The copolymer of octyl acrylamide/acrylate/methacrylic acid fourth amino ethyl ester | 0~30% | 15 | 10~100 |
Filler | Aluminium oxide | 0~20% | 10 | 5~100 |
Processing aid | Sorbitan trioleate paraffin | 0~2% | 0.07 0.03 | |
Fiber-enhancing-stable | Polyamide short fibre | 0~5% | 0.5 | 50~180 |
Fluid | ||||
Water | Water | 50~80% | 77.9 | |
First solvent | Ethanol | 0~25% | 16 | |
Second solvent | Methyl-sulfoxide | 0~25% | 1 | |
Surfactant | 2,4,7,9-tetramethyl-5-decine-4, the ethoxylate of 7-glycol | 0~2% | 0.1 | |
Rheology modifiers | PVP | 0~5% | 0.5% | |
Amine | One isopropanolamine | 0~15% | 5% |
Table 2
Component | Preferred compound | Acceptable compositing range (wt.%) | Preferred form (wt.%) | Particle size range (μ m) |
Embodiment 1 Granulate mixture | ||||
Thermoplastic | Polymethyl methacrylate | 50~100% | 88.9 | 10~100 |
Filler | Aluminium oxide | 0~20% | 10 | 5~100 |
Processing aid | Sorbitan trioleate paraffin | 0~2% | 0.07 0.03 | |
Fiber-enhancing-stable | Polyamide short fibre | 0~5% | 1.0 | 50~180 |
Fluid | ||||
First solvent | Dimethyl succinate | 100% | 100% |
Embodiment 2 Granulate mixture | ||||
Thermoplastic | Polyvinyl butyral resin | 50~100% | 98.9 | 10~100 |
Processing aid | Anhydro sorbitol Triolein paraffin | 0~2% | 0.07 0.03 | |
Fiber-enhancing-stable | Polyamide short fibre | 0~5% | 1.0 | 50~180 |
Fluid | ||||
First solvent | Methyl alcohol | 100% | 100% |
Component | Preferred compound | Acceptable compositing range (wt.%) | Preferred form (wt.%) | Particle size range (μ m) |
Embodiment 3 Granulate mixture | ||||
Thermoplastic | Polyamide 12 | 20~50% | 30% | 10~100 |
Inorganic bond | Gypsum | 50~80% | 65% | 5~100 |
Organic bond | Maltodextrin | 0~10% | 5% | 10~100 |
Fluid | ||||
First solvent | Water | 80~100% | 94.9% | |
Second solvent | Glycerine | 0~10% | 5% | |
Surfactant | 2,4,7,9-tetramethyl-5-decine-4, the ethoxylate of 7-glycol | 0~1% | 0.1% |
The flow hardening agent
Described fluid can comprise processing aid, as the flow hardening agent.The flow hardening agent can have some wet performance, but the hydrodynamic performances or the wetting characteristics of mainly still regulating fluid, so that the fluid volume that print head is carried maximization.The flow reinforcement is considered to a kind of viscoelastic phenomenon, and it has increased fluid flow, allows the thicker layer of printing, thereby allows more promptly to make up end article.Preferred compositions perhaps by the minimizing fluid viscosity, thereby increases fluid flow by reducing the friction between fluid and the shower nozzle wall, and it comprises oxalic acid second diester, potassium sorbate, and alum.Other compound that is suitable for use as the flow hardening agent can be selected from following non-limiting group: isopropyl alcohol, ethylene glycol monobutyl ether (EGMBE), the diethylene glycol monobutyl ether, lauryl dimethyl propane sulfonic acid ammonium, glyceryl triacetate, ethyl acetoacetate and comprise the water-soluble polymer of PVP, polyethylene glycol, polyacrylic acid and the Sodium Polyacrylate of about 30,000 units of molecular weight.For the ionomer such as Sodium Polyacrylate, the increase of flow changes with pH.
Dyestuff and pigment
Fluid of the present invention preferably contains dyestuff or pigment, thereby helps for the operator provides vision when making up goods.Dyestuff or pigment provide the difference between the powder of activating and be not activated, and make and can control printed layers when the operator makes up goods.Dyestuff or pigment include but not limited to naphthol blue black, and is Congo red, and such as the dispersion of the organic pigment of the cationic surface modification of copper phthalocyanine and carbon black.With a large amount of other dyestuffs and the pigment of described fluid compatible be that those skilled in the art are known.
Material of the present invention and method provide in a large number than the advantage that has the three dimensional printing method now.The used material of the present invention is cheap, allows to produce to have the firm of excellent surface smoothness and the goods of thin-walled.In addition, activate fluid and can contain and have high boiling component, prevented that the shower nozzle of print head is dry too early.
The used equipment of the inventive method is reliable, cheap, be easy to safeguard, makes it to be ideally suited in the office environment.Material that the present invention is used and ink-jet technology highly compatible.Like this, need less equipment to safeguard, increased the reliability of equipment.Therefore, method of the present invention comprises than shorter structure time of art methods and labour intensity still less.
Those skilled in the art should be readily appreciated that all listed parameters all are exemplary here, and actual parameter depends on the concrete purposes that the inventive method and material are used.Therefore, should be appreciated that previous embodiments only proposes as example, in the scope of appended claims and equivalent thereof, mask body was described and implement before the present invention can be different from.
Claims (87)
1, a kind of powder that is suitable for three dimensional printing, this powder comprises the blend of thermoplastic granulates thing and adhesive particle thing, wherein, the adhesive particle thing is suitable for when fluid activates this adhesive particle thing, bonding this thermoplastic granulates thing.
2, powder according to claim 1, wherein fluid is moisture.
3, powder according to claim 2, wherein the adhesive particle thing comprises the thermoplastic granulates thing, thereby this thermoplastic granulates thing activates in fluid slightly soluble and band viscosity at least at this, and when fluid by being partly dissolved the thermoplastic granulates thing at least during activation heat plastic particle thing, this thermoplastic granulates thing is suitable for bonding together, and this thermoplastic granulates thing is selected from: acetal polyformaldehyde, polyactide, polyethylene, polypropylene, ethylene vinyl acetate, polyphenylene oxide, ethylene-acrylic acid copolymer, polyether block amide, polyvinylidene fluoride, polyether-ketone, polybutylene terephthalate, PET, poly terephthalic acid cyclohexylidene methylene ester, polyphenylene sulfide, polythalamide, polymethyl methacrylate, polysulfones, polyether sulfone, PPSU, polyacrylonitrile, poly-(acrylonitrile-butadiene-styrene (ABS)), polyamide, the melocol condensation polymer, polystyrene, polyolefin, polyvinyl butyral resin, Merlon, polyvinyl chloride, PET, ethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, methylcellulose, cellulose acetate, hydroxypropyl methylcellulose, hydroxy butyl methyl cellulose, HEMC, ethylhydroxyethylcellulose, cellulose xanthate, and their combination and copolymer.
4, powder according to claim 2, wherein the fluid of activation heat plastic particle thing is suitable for by being exposed at least a curing the in ultraviolet light, visible light, heat, electron beam and the combination thereof.
5, powder according to claim 1, wherein fluid is non-moisture.
6. powder according to claim 5, wherein fluid is non-halo.
7, powder according to claim 1, wherein the thermoplastic granulates thing comprises the particle of the about 10 μ m of average particulate diameter~about 100 μ m.
8, powder according to claim 1, wherein the thermoplastic granulates thing comprises the thermoplastic that is selected from following material: acetal polyformaldehyde, polyactide, polyethylene, polypropylene, ethylene vinyl acetate, polyphenyl alkene ether, ethylene-acrylic acid copolymer, polyether block amide, polyvinylidene fluoride, polyether-ketone, polybutylene terephthalate, PET, poly terephthalic acid cyclohexylidene methylene ester, polyphenylene sulfide, pol1ythalamide, polymethyl methacrylate, polysulfones, polyether sulfone, PPSU, polyacrylonitrile, poly-(acrylonitrile-butadiene-styrene (ABS)), polyamide, melocol condensation polymer, polystyrene, polyolefin, polyvinyl butyral resin, Merlon, polyvinyl chloride, PET, ethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, methylcellulose, cellulose acetate, hydroxypropyl methylcellulose, hydroxy butyl methyl cellulose, HEMC, ethylhydroxyethylcellulose, cellulose xanthate, and their combination and copolymer.
9, powder according to claim 1, wherein the adhesive particle thing comprises the particle of the about 10 μ m of average particulate diameter~about 100 μ m.
10, powder according to claim 1, but wherein the adhesive particle thing comprises the resin of the resin that is selected from water-soluble resin and alkaline reduction, and also fluid activates this adhesive particle thing by the dissolved adhesive particle.
11, powder according to claim 10, wherein resin is selected from maltodextrin, polyvinyl alcohol, sulfonated polyester polymer, sulfonated polystyrene, the copolymer of octyl acrylamide/acrylate/methacrylic acid fourth amino ethyl ester, the copolymer of acrylate/octyl acrylamide, polyacrylic acid, PVP, the polyacrylic acid of styreneization, PEO, Sodium Polyacrylate, the copolymer of Sodium Polyacrylate and maleic acid, the copolymer of PVP and vinylacetate, butylated PVP, the copolymer of polyvinyl alcohol and vinylacetate, starch, modified starch, cationic starch, the starch of pre-gelatinization, the modified starch of pre-gelatinization, the cationic starch of pre-gelatinization, and their combination and copolymer.
12, powder according to claim 1, wherein the adhesive particle thing comprises inorganic bond.
13, powder according to claim 12, wherein inorganic bond is selected from gypsum, bentonite, precipitated silicate sodium, unbodied precipitated silica, unbodied precipitated silicate calcium, unbodied precipitated silicate magnesium, unbodied precipitated silicate lithium, salt, portland cement, magnesium phosphate cement, magnesium oxychloride cement contains oxygen magnesium sulfate cement, trbasic zinc phosphate cement, zinc oxide-eugenol cement, aluminium hydroxide, magnesium hydroxide, calcium phosphate, sand, wollastonite, dolomite, contain sodium ion, lithium ion, magnesium ion, with the amorphous sediment silicate of at least two kinds of ions in the calcium ion and their combination.
14, powder according to claim 1, it further comprises filler.
15, powder according to claim 14, wherein filler comprises inorganic substances.
16, powder according to claim 15, wherein inorganic substances are selected from aluminium oxide, soda-lime glass, borosilicate glass, silica, alumino-silicate pottery, lime stone, gypsum, bentonite, precipitated silicate sodium, unbodied precipitated silica, unbodied precipitated silicate calcium, unbodied precipitated silicate magnesium, unbodied precipitated silicate lithium, salt, portland cement, magnesium phosphate cement, magnesium oxychloride cement contains oxygen magnesium sulfate cement, trbasic zinc phosphate cement, zinc oxide-eugenol cement, aluminium hydroxide, magnesium hydroxide, calcium phosphate, sand, wollastonite, dolomite, contain sodium ion, lithium ion, magnesium ion, with the amorphous sediment silicate of at least two kinds of ions in the calcium ion and their combination.
17, powder according to claim 14, wherein filler comprises organic substance.
18, powder according to claim 17, wherein organic substance comprises carbohydrate.
19, powder according to claim 18, wherein carbohydrate is selected from starch, modified starch, cellulose, maltodextrin, acacin, locust bean gum, the starch of pre-gelatinization, the acid modified starch, hydrolyzed starch, sodium carboxymethylcellulose, mosanom, hydroxypropyl cellulose, methylcellulose, chitosan, carrageenan, pectin, agar, gellan gum, Arabic gum, xanthans, propylene glycol alginate, guar gum and their combination.
20, powder according to claim 17, wherein organic substance comprises protein.
21, powder according to claim 20, wherein organic substance is selected from gelatin, rabbit skin glue, soybean protein and their combination.
22, powder according to claim 1, it further comprises processing aid.
23, powder according to claim 1, it further comprises fortifying fibre.
24, powder according to claim 1, it further comprises filler and processing aid.
25, a kind of fluid that is used for three dimensional printing, this fluid comprises: have first solvent of first boiling point, wherein this fluid is suitable for activating the adhesive in the powder of the blend that comprises thermoplastic granulates thing and adhesive particle thing.
26, fluid according to claim 25, wherein this fluid is suitable for activating this adhesive by the dissolved adhesive particle.
27, fluid according to claim 25, wherein first solvent is selected from ethanol, isopropyl alcohol, normal propyl alcohol, methyl alcohol, n-butanol, glycol, ester, glycol ethers, ketone, aromatic compounds, aliphatic compounds, sprotic polar solvent, terpenes, acrylate, methacrylate, vinyl ethers, oxetanes, epoxide, low-molecular weight polymer, carbonic ester, N-methyl pyrrolidone, acetone, MEK, dibasic ester, ethyl acetate, dimethyl sulfoxide (DMSO), dimethyl succinate and their combination.
28, fluid according to claim 25, it further comprises second solvent with second boiling point.
29, fluid according to claim 28, wherein second boiling point is higher than first boiling point.
30, fluid according to claim 28, wherein second solvent is mixable with water.
31, fluid according to claim 30 wherein is selected from butyrolactone, carbonic acid glyceride, propylene carbonate with mixable second solvent of water, ethylene carbonate, dimethyl succinate, methyl-sulfoxide, N-methyl pyrrolidone, glycerine, 1,4-butanediol, polyethylene glycol, butyl carbitol, ethylene glycol, diethylene glycol (DEG), propane diols, polypropylene glycol, polyglycol ether, polypropylene glycol ether, tetraethylene glycol ether, butylene carbonate, pentanediol, hexylene glycol and their combination.
32, fluid according to claim 25, it further comprises water.
33, fluid according to claim 32, wherein first solvent is mixable with water.
34, fluid according to claim 32, it further comprises second solvent with second boiling point, wherein, second solvent is mixable with water.
35, fluid according to claim 34, wherein second boiling point is higher than first boiling point.
36, fluid according to claim 25, it further comprises surfactant.
37, fluid according to claim 25, it further comprises rheology modifiers.
38, fluid according to claim 25, it further comprises amine.
39, according to the described fluid of claim 38, wherein amine is selected from monoisopropanolamine, triethylamine, 2-amino-2-methyl-1-propanol, 1-amino-2-propyl alcohol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol, N, N-diethyl ethylene diamine, N methyldiethanol amine, N, N-dimethylethanolamine, triethanolamine, the 2-ethylaminoethanol, two [3-(dimethylamino) propyl group] amino of 1-[]-the 2-propyl alcohol, 3-amino-1-propyl alcohol, 2-(2-aminoethyl amino) ethanol, three (methylol) aminomethane, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, diethanol amine, 1, two (the dimethylamino)-2-propyl alcohol of 3-, ammonium hydroxide, MEA, aminomethyl propanol, aminoethyl ethanolamine, triisopropanolamine, PPOX triamine, polymine and their combination.
40, a kind of fluid that is used for three dimensional printing, this fluid comprises solvent, wherein fluid is suitable for activating the bond properties of sl. sol. at least thermoplastic granulates thing.
41, according to the described fluid of claim 40, wherein fluid is non-moisture.
42, according to the described fluid of claim 41, wherein fluid is non-halo.
43, according to the described fluid of claim 42, wherein solvent is selected from alcohol, glycol, ester, glycol ethers, ketone, aromatic compounds, aliphatic compounds, sprotic polar solvent, terpenes, acrylate, methacrylate, vinyl ethers, oxetanes, epoxide, low-molecular weight polymer, carbonic ester and their combination.
44, according to the described fluid of claim 43, wherein alcohol is selected from methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol and their combination.
45, according to the described fluid of claim 43, wherein glycol is selected from ethylene glycol, diethylene glycol (DEG), propane diols, polyethylene glycol, butanediol, pentanediol, hexylene glycol and their combination.
46, according to the described fluid of claim 43, wherein ester is selected from ethyl acetate, acetate propylene glycol monomethyl ether ester, pentyl acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, acetate DEGMBE ester, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-butyl acetate, tert-butyl acetate, acetate 2-Octyl Nitrite, oxalic acid second diester, diethyl succinate, methyl lactate, ethyl lactate, dimethyl tartrate, ethyl tartrate and their combination.
47, according to the described fluid of claim 43, wherein glycol ethers is selected from the dipropylene glycol methyl ether, diglycol butyl ether, diglycol one ether, propylene glycol monomethyl ether, glycol propyl ether and their combination.
48, according to the described fluid of claim 43, wherein ketone is selected from acetone, MEK, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl n-pro-pyl ketone, methyl isoamyl ketone, methyl-n-amyl ketone, DIBK and their combination.
49, according to the described fluid of claim 43, wherein aromatic compounds is selected from toluene, dimethylbenzene, phenol, benzene, styrene, the aromatic petroleum naphtha of high-flash and their combination.
50, according to the described fluid of claim 43, wherein aliphatic compounds are selected from hexane, heptane, cyclohexane and their combination.
51, according to the described fluid of claim 43, wherein sprotic polar solvent is selected from the N-methyl pyrrolidone, methyl-sulfoxide, 2-Pyrrolidone, butyrolactone and their combination.
52, according to the described fluid of claim 43, wherein terpenes comprises citrene.
53, according to the described fluid of claim 43, wherein acrylate is selected from oxyalkylated bifunctional acrylate, acrylic acid 2-phenoxy ethyl, tetrahydrofurfuryl acrylate, acrylic acid 2 (2 ethoxy ethoxy) ethyl ester, the own diester of diacrylate, new penta diester of propenoxylated diacrylate, lauryl acrylate, isodecyl acrylate, acrylic acid ester in three last of the ten Heavenly stems, isobornyl acrylate, diacrylate three propylene diesters, acrylic acid octadecane ester, allyl acrylate, Isooctyl acrylate monomer, the acrylic acid caprolactone, the alkoxylate tetrahydrofurfuryl acrylate, diacrylate fourth diester, diacrylate 1,3-fourth diester, diacrylate diethyl diester, diacrylate is gathered second diester, the own diester of alkoxylate diacrylate, oxyalkylated diacrylate cyclohexane dimethyl ester, diacrylate cyclohexane dimethyl ester, dipropylene glycol diacrylate, the diacrylate bisphenol-A ester of ethoxylation, new penta diester of diacrylate, oxyalkylated aliphatic diacrylate, three acrylic acid trimethyl propyl ester, three (2-hydroxyethyl) isocyanuric acid ester triacrylate, three acrylic acid trimethyl propyl ester of ethoxylation, propenoxylated three acrylic acid trimethyl propyl ester, propenoxylated three acrylic acid glyceride, pentaerythritol tetracrylate, pentaerythritol triacrylate, tetrapropylene acid two trimethyl propyl ester, five acrylic acid dipentaerythritol ester, the pentaerythritol tetracrylate of ethoxylation, oxyalkylated acrylic acid nonyl benzene phenolic ester and their combination.
54, according to the described fluid of claim 43, wherein methacrylate is selected from methacrylic acid 2-ethyl phenoxy, tetrahydrofurfuryl methacrylate, the own diester of dimethacrylate, lauryl methacrylate, isodecyl methacrylate, methacrylic acid ester in three last of the ten Heavenly stems, isobornyl methacrylate, monomethyl acrylic acid propylene diester, methacrylic acid octadecane ester, allyl methacrylate, EHMA, tetramethylene dimethacrylate, dimethacrylate 1,3-fourth diester, dimethacrylate second diester, dimethacrylate diethyl diester, dimethacrylate three second diester, dimethacrylate tetrem diester, dimethacrylate gathers second diester, dimethacrylate cyclohexane dimethyl ester, dimethacrylate two propylene diesters, the dimethacrylate bisphenol-A ester of ethoxylation, new penta diester of dimethacrylate, trimethyl acrylic acid trimethyl propyl ester, the methacrylic acid methoxy gathers the second diester, oxyalkylated methacrylic acid nonyl benzene phenolic ester, the hydroxyethyl methacrylate of ethoxylation, allyl methacrylate, propenoxylated allyl methacrylate and their combination.
55, according to the described fluid of claim 43, therein ethylene base ether is selected from hydroxy butyl vinyl ether, the triethylene glycol divinyl ether, cyclohexyl dimethanol divinyl ether, the propenyl ether of propylene carbonate, dodecyl vinyl, cyclohexane methanol one vinyl ethers, cyclohexyl vinyl ether, diethylene glycol divinyl ether, 2-ethylhexyl vinyl ethers, the dipropylene glycol divinyl ether, the tripropylene glycol divinyl ether, hexylene glycol divinyl ether, octadecyl vinyl ether, the butanediol divinyl ether, two [4-(ethyleneoxy) butyl] esters of M-phthalic acid, two [4-(ethyleneoxy) butyl] ester and their combinations of adipic acid.
56, according to the described fluid of claim 43, wherein oxetanes is selected from 3-ethyl-3-methylol-oxetanes, and 1, two [(3-ethyl-3-oxa-cyclobutyl methoxy base) methyl] benzene and their combinations of 4-.
57, according to the described fluid of claim 43, wherein epoxide is selected from 3,4-epoxycyclohexyl methyl-3, and the 4-epoxycyclohexane carboxylate, adipic acid is two-(3, the 4-epoxycyclohexyl) ester, an oxidation citrene, 1,2-epoxy hexadecane and their combination.
58, according to the described fluid of claim 43, wherein low-molecular weight polymer comprises polymine.
59, according to the described fluid of claim 43, wherein carbonic ester comprises ethylene carbonate, propylene carbonate, butylene carbonate, carbonic acid glyceride and their combination.
60, a kind of fluid that is used for three dimensional printing, this fluid comprise water and have second solvent of second boiling point, and wherein, this fluid is suitable for activating the adhesive in the powder of the blend that comprises thermoplastic granulates thing and adhesive particle thing.
61, according to the described fluid of claim 60, wherein second solvent is selected from butyrolactone, carbonic acid glyceride, propylene carbonate, ethylene carbonate, dimethyl succinate, methyl-sulfoxide, N-methyl pyrrolidone, glycerine, 1,4-butanediol, polyethylene glycol, butyl carbitol, ethylene glycol, diethylene glycol (DEG), propane diols, polypropylene glycol, polyglycol ether, polypropylene glycol ether, tetraethylene glycol ether, butylene carbonate, pentanediol, hexylene glycol and their combination.
62, according to the fluid of claim 60, it further comprises surfactant.
63, according to the fluid of claim 60, it further comprises rheology modifiers.
64, according to the fluid of claim 60, it further comprises first solvent with first boiling point, and wherein, first boiling point is lower than second boiling point.
65. according to the described fluid of claim 64, wherein first solvent is selected from ethanol, isopropyl alcohol, normal propyl alcohol, methyl alcohol, n-butanol, glycol, ester, glycol ethers, ketone, aromatic compounds, aliphatic compounds, sprotic polar solvent, terpenes, acrylate, methacrylate, vinyl ethers, oxetanes, epoxide, low-molecular weight polymer, carbonic ester, acetone, ethyl acetate, dimethyl succinate and their combination.
66, according to the described fluid of claim 60, it further comprises amine.
67, according to the fluid of claim 66, wherein amine is selected from monoisopropanolamine, triethylamine, 2-amino-2-methyl-1-propanol, 1-amino-2-propyl alcohol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol, N, N-diethyl ethylene diamine, N methyldiethanol amine, N, N-dimethylethanolamine, triethanolamine, the 2-ethylaminoethanol, two [3-(dimethylamino) propyl group] amino of 1-[]-the 2-propyl alcohol, 3-amino-1-propyl alcohol, 2-(2-aminoethyl amino) ethanol, three (methylol) aminomethane, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, diethanol amine, 1, two (the dimethylamino)-2-propyl alcohol of 3-, ammonium hydroxide, MEA, aminomethyl propanol, aminoethyl ethanolamine, triisopropanolamine, PPOX triamine, polymine and their combination.
68, a kind of fluid that is used for three dimensional printing, this fluid comprises water and amine, wherein, but this fluid is suitable for activating the bond properties of sl. sol. at least alkaline reduction particle.
69, according to the described fluid of claim 68, wherein amine is selected from monoisopropanolamine, triethylamine, 2-amino-2-methyl-1-propanol, 1-amino-2-propyl alcohol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol, N, N-diethyl ethylene diamine, N methyldiethanol amine, N, N-dimethylethanolamine, triethanolamine, the 2-ethylaminoethanol, two [3-(dimethylamino) propyl group] amino of 1-[]-the 2-propyl alcohol, 3-amino-1-propyl alcohol, 2-(2-aminoethyl amino) ethanol, three (methylol) aminomethane, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, diethanol amine, 1, two (the dimethylamino)-2-propyl alcohol of 3-, ammonium hydroxide, MEA, aminomethyl propanol, aminoethyl ethanolamine, triisopropanolamine, PPOX triamine, polymine and their combination.
70, according to the described fluid of claim 68, it further comprises first solvent with first boiling point.
71, according to the described fluid of claim 70, wherein first solvent is selected from ethanol, isopropyl alcohol, normal propyl alcohol, methyl alcohol, n-butanol, glycol, ester, glycol ethers, ketone, aromatic compounds, aliphatic compounds, sprotic polar solvent, terpenes, acrylate, methacrylate, vinyl ethers, oxetanes, epoxide, low-molecular weight polymer, carbonic ester, acetone, ethyl acetate, dimethyl succinate and their combination.
72, according to the described fluid of claim 70, it further comprises second solvent with second boiling point, and wherein second boiling point is higher than described first boiling point.
73, according to the described fluid of claim 72, wherein second solvent is selected from butyrolactone, carbonic acid glyceride, propylene carbonate, ethylene carbonate, dimethyl succinate, methyl-sulfoxide, N-methyl pyrrolidone, glycerine, 1,4-butanediol, polyethylene glycol, butyl carbitol, ethylene glycol, diethylene glycol (DEG), propane diols, polypropylene glycol, polyglycol ether, polypropylene glycol ether, tetraethylene glycol ether, butylene carbonate, pentanediol, hexylene glycol and their combination.
74, according to the described fluid of claim 68, it further comprises surfactant.
75, according to the described fluid of claim 68, it further comprises rheology modifiers.
76, a kind of method by three dimensional printing formation goods, this method comprises the following steps:
A large amount of adjacent particle are provided, and this particle has the average diameter of about 10 μ m~about 100 μ m, and described particle comprises the blend of thermoplastic granulates thing and adhesive particle thing; With
Fluid is put on these a large amount of particles, wherein the adhesive particle thing is solvable to small part in this fluid, the thermoplastic granulates thing is basic inertia in this fluid, this fluid makes the adhesive particle thing activate from the state of basic inertia, the activation amount is enough to these a large amount of particle bond are arrived together, is essentially the single goods of solid with qualification.
77, according to the described method of claim 76, it further comprises these goods of heating, so that this thermoplastic granulates thing of small part sintering.
78, a kind of method by three dimensional printing formation goods, this method comprises the following steps:
A large amount of adjacent particle are provided, and this particle has the average diameter of about 10 μ m~about 100 μ m, and described particle comprises the blend of thermoplastic granulates thing and adhesive particle thing; With
Fluid is put on these a large amount of particles, wherein the adhesive particle thing is partly soluble at least in this fluid, the thermoplastic granulates thing is basic inertia in this fluid, this fluid dissolved adhesive particle, its meltage is enough to these a large amount of particle bond are arrived together, is essentially the single goods of solid with qualification.
79, according to the described method of claim 78, it further comprises these goods of heating, so that this thermoplastic granulates thing of small part sintering.
80, a kind of method by three dimensional printing formation goods, this method comprises the following steps:
But in the first of the first film of the particle that comprises a large amount of thermoplastic granulates and activated adhesive, apply aqueous fluid, this fluid is with the amount activated adhesive of the single goods that are essentially solid that are enough to form bonded particulate;
On the first film, form second film of this particle; With
In the first of second film of particle, apply aqueous fluid, present in an amount at least sufficient to activated adhesive, make the particle in the first of second film be adhered to one another, and be bonded at least a portion of first of the first film, to form the single goods that are essentially solid from the first of the first film and the first of second film.
81,0 described method according to Claim 8, it further comprises these goods of heating, so that this thermoplastic granulates thing of small part sintering.
82, a kind of method by three dimensional printing formation goods, this method comprises the following steps:
In the first of the first film of the particle that comprises a large amount of thermoplastic granulates, apply non-moisture fluid, this fluid is with the surface of the amount activation heat plastic particle of the single goods that are essentially solid that are enough to form bonded particulate;
On the first film, form this particle second film and
In the first of second film of particle, apply this non-aqueous fluid, present in an amount at least sufficient to the surface of activation heat plastic particle, make the particle in the first of second film be adhered to one another, and be bonded at least a portion of first of the first film, to form the single goods that are essentially solid from the first of the first film and the first of second film; With
On printed layers, apply at least a in ultraviolet light, visible light, heat and the electron beam, solidify to induce non-aqueous fluid.
83, a kind of goods comprise the product of following material:
Powder, this powder contain (i) thermoplastic granulates thing and (ii) adhesive particle thing; With
Fluid, this fluid activated adhesive particle comprises the goods of the solid basically of powder with formation, and this adhesive particle thing dissolves in this fluid basically,
Wherein, these goods comprise a large amount of adjacent layers that formed by this product, and every layer has the profile that limits the edge and comprises each edge limited goods net shape by these layers.
84,3 described goods according to Claim 8, wherein powder comprises filler.
85,3 described goods according to Claim 8, wherein powder comprises processing aid.
86,3 described goods according to Claim 8, wherein goods further comprise bleeding agent.
87,6 goods according to Claim 8, wherein bleeding agent is selected from the epoxy-amine system, free radical ultraviolet curing acrylic ester system, cation ultraviolet cured epoxy system, the bi-component carbamate system that comprises isocyanates-polyalcohol and isocyanates-amine, cyanoacrylate and their combination.
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EP (2) | EP2269808B1 (en) |
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AU (1) | AU2004249662A1 (en) |
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Also Published As
Publication number | Publication date |
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US20050003189A1 (en) | 2005-01-06 |
EP1628823B8 (en) | 2012-06-27 |
JP4662942B2 (en) | 2011-03-30 |
EP2269808B1 (en) | 2017-03-22 |
EP2269808A1 (en) | 2011-01-05 |
KR101120156B1 (en) | 2012-02-22 |
AU2004249662A1 (en) | 2004-12-29 |
US7569273B2 (en) | 2009-08-04 |
EP1628823B1 (en) | 2011-10-26 |
KR101148770B1 (en) | 2012-05-24 |
KR20060022243A (en) | 2006-03-09 |
HK1152678A1 (en) | 2012-03-09 |
CA2526100A1 (en) | 2004-12-29 |
HK1092420A1 (en) | 2007-02-09 |
JP2007502713A (en) | 2007-02-15 |
CN100553949C (en) | 2009-10-28 |
WO2004113042A2 (en) | 2004-12-29 |
ES2376237T3 (en) | 2012-03-12 |
EP1628823A2 (en) | 2006-03-01 |
ATE530331T1 (en) | 2011-11-15 |
WO2004113042A3 (en) | 2005-12-08 |
KR20110054037A (en) | 2011-05-24 |
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